CN102203218B - Method and apparatus for manufacturing biodiesel fuel, and decomposition catalyst for decarboxylation of fats used in the method - Google Patents
Method and apparatus for manufacturing biodiesel fuel, and decomposition catalyst for decarboxylation of fats used in the method Download PDFInfo
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- CN102203218B CN102203218B CN200980143059.3A CN200980143059A CN102203218B CN 102203218 B CN102203218 B CN 102203218B CN 200980143059 A CN200980143059 A CN 200980143059A CN 102203218 B CN102203218 B CN 102203218B
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- catalyst
- grease
- oil
- decarboxylation
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- 239000002440 industrial waste Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
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- 150000002602 lanthanoids Chemical class 0.000 description 1
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- 150000002617 leukotrienes Chemical class 0.000 description 1
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- 244000144972 livestock Species 0.000 description 1
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- 229940062043 nitrogen 50 % Drugs 0.000 description 1
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- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 239000003346 palm kernel oil Substances 0.000 description 1
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- 239000003208 petroleum Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 150000003904 phospholipids Chemical class 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 235000013324 preserved food Nutrition 0.000 description 1
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- 238000010298 pulverizing process Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
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- 229910052701 rubidium Inorganic materials 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
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- 229910052710 silicon Inorganic materials 0.000 description 1
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- 239000010802 sludge Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
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Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/14—Silica and magnesia
-
- 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
- C10G3/42—Catalytic treatment
- C10G3/44—Catalytic treatment characterised by the catalyst used
- C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
- C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
-
- 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
- C10L1/08—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for compression ignition
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/10—Magnesium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Liquid Carbonaceous Fuels (AREA)
- Catalysts (AREA)
Abstract
Provided is a method for manufacturing biodiesel fuel, which makes it possible to construct a distributed energy supply system that provides needed energy to locations that require the energy. The system is characterized by excellent storage stability, such that alcohol (subsidiary raw material) is not required, glycerin is not produced as a by-product, impurities such as dienes are unlikely to remain in the product, the amount of coke generated is small, the pour point is low, and blackening and abnormal odors rarely occur due to stability against air. The system is also characterized by excellent production efficiency and productivity which prevent running costs from increasing or productivity from decreasing due to secondary tasks such as treatment and reactivation of used catalysts. The system is further characterized by enabling a simplified manufacturing process and a simplified reactor without the need for pretreatment to remove free fatty acids from raw material fats. At 350 DEG C to 475 DEG C, a decomposition catalyst for fat decarboxylation and fats are brought into contact, an ester binding portion is cleaved in a decarboxylation reaction under the action of the decomposition catalyst for fat decarboxylation, and biodiesel fuel formed mainly from C8 to C24 hydrocarbons is obtained.
Description
[technical field]
The present invention relates to method and the preparation facilities thereof of efficiently preparing high-quality biodiesel fuel from grease or oil expression raw material.In addition, also relate to for this preparation method and preparation facilities, the grease decarboxylation decomposition catalyst of good efficiency.
[background technology]
In order to reduce the discharge rate of greenhouse effects of the earth gas and Air Pollutants, construct energy Circular Society Construction, biodiesel fuel is very important technology.As the preparation method of this biodiesel fuel, fatty acid methyl ester (FAME:fatty acid methyl ester) method of changing extensively is introduced.Methyl esterification of fatty acid method is by making raw oil material and low-carbon alcohols (auxiliary material) carry out ester exchange reaction, obtains the method (non-patent literature 1) of fuel used for diesel engine.
As the technology relevant to methyl esterification of fatty acid method, (patent document 1) discloses " carrying out under the existence of calcium system solid catalyst by making grease and low-carbon alcohols reacting the method preparing fatty acid alkyl esters ".
In addition, (patent document 2) discloses " preparation method of biodiesel; it has following operation: by making raw oil material and alcohol react under the existence of solid acid catalyst, the free fatty existed is changed into the operation A of fatty acid alkyl esters in raw oil material; Dewatered process B in the reactant mixture obtained from operation A; And the liquid that obtains in process B and alcohol are reacted under the existence of solid base catalyst, make the triacylglycerol ester generation ester exchange reaction as raw oil material principal component, change the operation C of fatty acid alkyl esters into ".
As the preparation method of other biodiesel fuel, the hydroprocessing process that known (non-patent literature 1) is recorded.Hydroprocessing process is a kind of application method belonging to the hydrogen addition technology of petroleum refining process in the past, the method is by carrying out hydrotreatment under the high pressure of 10MPa, the oxygen in raw oil material is made to depart from mainly as water and reach lighting, simultaneously by the unsaturated bond saturation from raw oil material, obtain the method for the hydrocarbon ils in light oil (1ight oil) boiling range.
In addition, (patent document 3) discloses " use one to have the fluidized catalytic cracker of conversion zone, segregation section, stripping (stripping) section and regenerator section; in the conversion zone of outlet temperature 480 ~ 540 DEG C; make the feedstock oil containing living beings contact for 1 ~ 3 second with the solid acid catalyst such as ultrastable or silica alumina, obtain the processing method of the living beings of gasoline base or diesel fuel base etc. ".
And then, (patent document 4) discloses " by solid acid catalyst in reaction vessel, heat in the temperature province of 350 ~ 450 DEG C; make this solid acid catalyst contact with liquid fat; to remove oxydant from above-mentioned grease, synthesizing with the catalyst cracking method of the grease of the alkene of carbon number 9 ~ 24 and the alkane hydrocarbon mixture that is principal component ".
[prior art document]
[patent document]
[patent document 1] JP 2008-143983 publication
[patent document 2] JP 2008-1856 publication
[patent document 3] JP 2007-177193 publication
No. 2008-086034, [patent document 4] Patent
[non-patent literature]
[non-patent literature 1] ENEOS Technical Review the 49th No. 2nd, volume (in June, 2007)
[summary of the invention]
Invent problem to be solved
But, in above-mentioned conventional art, have as following problem.
(1), in methyl esterification of fatty acid method disclosed in non-patent literature 1, patent document 1 and patent document 2, owing to needing a large amount of low-carbon alcohols, therefore there is the problem needing great number operating cost.In addition, generate in oil because the impurity (such as dienes, hydroxyl, peroxide etc.) in raw oil material easily remains in, therefore also exist and generate oil to instability such as air, lack the problem of stability in storage.In order to solve this problem, the adsorbents such as atlapulgite must be set using and carry out the impurity such as adsorbed peroxide with the operation it removed from generation oil, therefore there is the problem that treatment process is complicated.
(2), in methyl esterification of fatty acid method, owing to using the base catalyst as non-patent literature 1 record, therefore, there is the problem of by-product fatty acid soaps.If the by-product amount of fatty acid soaps is too much, aliphatic acid ester layer will be made to become difficulty with being separated of glycerin layer, cause fatty acid ester to be mixed in glycerin layer, thus cause fatty acid ester yield to reduce.In addition, owing to being dissolved with base catalyst (caustic soda etc.) in the glycerine of by-product, it is made to be treated as problem.It is indispensable that the treatment technology of by-product glycerin stands in the establishment of methyl esterification of fatty acid law technology really, but does not still establish effective treatment technology so far.
(3) in the methyl esterification of fatty acid method that patent document 1 is recorded, although the by-product amount of fatty acid soaps can be suppressed to low degree by using calcium system solid catalyst, but as other problem points, free fatty contained in raw material glyceryl ester can make the activity of solid catalyst reduce, and this is Problems existing.Its result, must use solid catalyst in a large number, thus produces a large amount of used catalyst, must carry out reactivation process etc. to used catalyst, there is the problem that Appendage Task increases, makes operating cost rise, productivity ratio be reduced simultaneously.
(4) due to suppress free fatty cause the reduction of the activity of solid base catalyst, therefore, patent document 2 disclose a kind of as front operation by processing free fatty with the technology it removed from raw oil material under the existence of solid acid catalyst.Technology disclosed in patent document 2, due to first free fatty will be processed under the existence of solid acid catalyst in operation A, and then under the existence of alcohol and solid base catalyst, make it react in operation C, so just need multiple operation, there is the problem that treatment process is complicated.
(5), in the hydroprocessing process that non-patent literature 1 is recorded, the freezing point of gained hydrocarbon ils is high, is+20 DEG C, there is the problem of poor fluidity.In addition, in the hydrocarbon ils obtained, be mixed into glycerine, there is the problem lacking stability.The freezing point of hydrocarbon ils is high, and this has problem when area cold especially uses, and now, the condition only reached by less than 5% is mixed into the degree used in light oil.
(6) technology disclosed in patent document 3 is the fluidized catalytic cracker that a kind of use has conversion zone, segregation section, stripping section and regenerator section, is obtained the technology of gasoline base etc. by grease.In this technology, process in the place concentrated raw oil material must be transported to existing for extensive fluidized catalytic cracker.But as department of botany's living beings of glyceride stock owing to being the dispersion Input-and-output-oriented resource using wide soil as production base, therefore, for delivering to the traffic requirements very high cost of concentration point and fluidized catalytic cracker, this is the problem existed.And, in order to reduce cost of transportation etc., in the construction of production base of department of botany's living beings only to prepare the large-scale fluidized catalytic cracker that biodiesel fuel is target, must therefore have problems such as making operating cost rising.In addition also there is following problem: if raw oil material touches solid acid catalyst in the conversion zone of outlet temperature 480 ~ 540 DEG C, key between the carbon of then alkyl easily ftractures, cause product degraded, thus the preparation amount of Fuel Petroleum base material is increased, the preparation amount of diesel fuel base reduces.In addition, in the reaction of solid acid catalyst, due to a lot of aromatic generation, the growing amount of coke (coke, the carbide generated on the catalyst of the hydro carbons such as process oil, also referred to as koks) is many, and the surface of solid acid catalyst is separated out, the activity of catalyst will reduce in the early stage, this is Problems existing, but also produces the problem being bonded to block by multiple catalyst, has the problem that yield reduces and operation change is difficult.And then the activity of catalyst is once reduce, and decarboxylation ability just decreases, the also easy impurity such as by-product carboxylic acid (free fatty), thus make the glossy black change of generation or produce foreign odor, these are all the problems existed.And there is the oily problem being not suitable for actual use of generation that acid is many, aromatic series is many, Cetane number is low.
(7) disclosed in patent document 4, technology is following technology: the solid acid catalyst by heating is contacted with grease, is obtained with the hydrocarbon mixture of the alkene of carbon number 9 ~ 24 and the alkane fuel used for diesel engine that is principal component by grease by catalytic cracking.Although this technology uses solid acid catalyst, adopt the reaction temperature also lower than patent document 3, this is relatively mild reaction condition, thus the fracture ratio between the carbon of alkyl can be made to reduce.But owing to remaining the reaction of solid acid catalyst, therefore, the growing amount of coke is many, the yield of kerosene light oil composition reduces, and easily makes the activity of catalyst reduce, and these are all the problems existed.And then the activity of catalyst is once reduce, and decarboxylation ability just decreases, the also easy impurity such as by-product carboxylic acid (free fatty), thus make the raw black change of generation fry dried food ingredients or produce foreign odor, these are all the problems existed.
The present invention is in order to solve above-mentioned problem in the past, its object is to, a kind of like this preparation method of biodiesel fuel is provided, the method does not need alcohol (auxiliary material), can not by-product glycerol, and dienes in raw oil material and hydroxyl, the impurity such as peroxide are difficult to remain in product, the growing amount of coke is few, pour point is also low, also the impurity such as by-product carboxylic acid (free fatty) are difficult to, therefore, air etc. is stablized, not easily there is black change or foreign odor, stability in storage is excellent, and, not easily produce the problem that catalyst activity that the free fatty due to by-product causes reduces, therefore the operating cost owing to processing used catalyst or needed for the Appendage Task such as reactivation can be reduced significantly, productivity ratio is excellent, and then do not need the pretreatment etc. removing free fatty from raw oil material, and can react at ambient pressure, therefore, the simplification of preparation section and the simplification of reaction unit can be sought, can in the place construction of necessity for supplying the dispersed-type power sources feed system of the necessary energy, even the raw material that unrighted acid is many, also high yield can be reached.In addition, the present invention also aims to, a kind of preparation facilities that can obtain the biodiesel fuel of the biodiesel fuel of high-quality with high yield from oil expression raw material or grease is provided.In addition, the present invention also aims to, there is provided a kind of can the double bond fracture of oil-control, promote decarboxylation decomposition reaction, thus can obtain by grease the grease decarboxylation decomposition catalyst used in the preparation method of the biodiesel fuel of the biodiesel fuel of high-quality efficiently.
For solving the means of problem
In order to solve above-mentioned problem in the past, the preparation method of biodiesel fuel of the present invention has following formation:
The preparation method of biodiesel fuel according to claim 1 of the present invention, the method has following formation: in 350 DEG C ~ 475 DEG C, in reaction vessel, make grease decarboxylation decomposition catalyst contact with grease, mainly generate C by above-mentioned grease decarboxylation decomposition catalyst with the decarboxylation decomposition reaction shown in formula (1)
8~ C
24hydrocarbon.
[changing 1]
Wherein, R
1, R
2, R
3be the alkyl forming grease, represent alkane, alkene.
C
xh
ythe mainly propane of carbon number 3, generates a small amount of methane, ethane, butane in addition.
According to this formation, the effect of the following stated can be obtained.
(1) at 350 DEG C ~ 475 DEG C, grease decarboxylation decomposition catalyst is contacted with grease, due to the effect of grease decarboxylation decomposition catalyst, the ester bond part of glycerine is ftractureed, cause the decarboxylation shown in (changing 1) to decompose, thus the decomposition gas (hydrocarbon) becoming biodiesel fuel can be obtained.Be explained, according to the kind of grease decarboxylation decomposition catalyst, also can consider preferentially to cause de-CO.As can be seen from the reaction shown in (change 1), due to not by-product glycerol, therefore, the treatment technology of glycerine and process man-hour etc. are not needed to establish.In addition, owing to obtaining the gaseous compound as the propane of accessory substance, methane, ethane, butane, therefore can use as gaseous fuel, also can as the fuel for heating needed for grease decarboxylation decomposition catalyst.
(2) this decarboxylation decompose due to be there is not alcohol actually condition under carry out, therefore, significantly can reduce operating cost, and the unstable impurity such as dienes in raw oil material and peroxide is easily decomposed on the surface at grease decarboxylation decomposition catalyst, therefore, not easily remain in product, also the not easily impurity such as by-product carboxylic acid (free fatty), therefore, can obtain stable to air etc. and the excellent biodiesel fuel of the stability in storage of black change or foreign odor not easily occurs.In addition, do not need by using adsorbent by the operation of the impurity absorption removings such as peroxide, economical yet.And then the growing amount of coke is few, therefore also not easily produces the activity separating out caused grease decarboxylation decomposition catalyst due to coke on catalyst surface and reduce and the problem such as grease decarboxylation decomposition catalyst caking, thus stable operation can be carried out with high yield.
(3) although there is free fatty in raw material, de-CO is carried out by the ester bond part cracking of the glycerine such as grease
2thus the not easily impurity such as by-product carboxylic acid (free fatty), even if by-product free fatty is also easily decomposed into hydrocarbon and carbon dioxide in reaction, therefore, the carboxylic acid (free fatty) of by-product not easily produces the problem that catalyst activity reduces.Therefore, even if part activity reduced is estimated to use catalyst in a large number interior also there is no need, thus can not rise owing to causing Appendage Tasks such as the process of used catalyst and reactivations operating cost or productivity ratio is reduced.Waste oil contains a large amount of free fatties with the grease (curcas oil: Jatropha wet goods) with a large amount of unsaturated bond due to oxidative degradation, and therefore the present invention is very effective to these greases.
(4) in using the decarboxylation of grease decarboxylation decomposition catalyst to decompose, the de-CO of glycerine is caused
2or de-CO, by reclaiming residual carbochain, hydrocarbon mainly as carbon number 8 ~ 24 can be obtained and freezing point at the excellent biodiesel fuel of the mobility of about-20 DEG C.
(5) owing to not needing the pretreatment etc. carrying out removing from raw oil material free fatty in order to prevent the activity of grease decarboxylation decomposition catalyst from reducing, and catalytic cracking operation can be carried out at ambient pressure, therefore, preparation section and the reaction unit of biodiesel fuel can be simplified, productivity ratio is excellent, meanwhile, biodiesel fuel can be prepared at low cost.Therefore, reaction unit can be built at low cost in the place of the production base of department of botany's living beings or necessity, can in the place construction of necessity for supplying the dispersed-type power sources feed system of the necessary energy.
(6) because grease decarboxylation decomposition catalyst is heated to 350 ~ 475 DEG C, therefore, the reaction speed that decarboxylation is decomposed is fast, can prepare using the alkene of carbon number 8 ~ 24 and alkane as the biodiesel fuel of principal component on high production rate ground.
(7) be liquid at 350 ~ 475 DEG C of greases, evaporate hardly.Therefore, product is only had to become gas and derived by from reaction vessel.
(8) there is thermal decomposition hardly at 350 ~ 475 DEG C of greases.Therefore, decompose because decarboxylation occurs grease major part, so can prevent from occurring degraded because of the fracture of double bond portions under heat.
(9) because product is derived by as gas, therefore, the phosphoric acid in raw material deposits on grease decarboxylation decomposition catalyst, transfers to hardly and decomposes in oil.Therefore, the performance that engine can not occur because phosphoric acid causes reduces and damage accident, thus can feel at ease to use decomposition oil.Particularly when using the high manioca of phosphorus acid content and fish pomace (or fish oil), soybean etc. as raw material, the present invention is also effective.
Herein, as grease, the rapeseed oil, palm oil, palm-kernel oil, olive oil, soybean oil, perilla herb oil, castor oil, curcas oil, the corn wet goods vegetable oil that extract oil and obtain can be used; The tallows etc. such as terpenes, fish oil, lard, butter; The grease extracted from some kind algae and their mixture.In addition, tempura wet goods waste edible oil can also be used.The greases such as ambient temperature curing lard, butter, can due to by the catalyst action that heats or be preheated melting and liquefied, and therefore, as grease, any one in liquid, solid-state all can use.
About grease, one or more mixture and catalyst exposure can be made and react.In addition, for grease, also before contacting the catalyst, at the temperature below 475 DEG C, preheating can be carried out.After catalyst exposure, decomposition efficiency can be improved by Fast Heating.
Grease is triacylglycerol (3 acyl groups and glycerine carry out ester and is combined into), and Phospholipids, glycolipid matter and aliphatic acid etc. also can use as raw material of the present invention.
The preferred alkalescent of grease decarboxylation decomposition catalyst, neutrality, weakly acidic catalyst.Specifically, more than a kind in the solid acid of the silica of solid catalyst, the carbon of activate, solid base, clay mineral, alkalosis can be used.As the carbon of activate, the carbide of the grain powdery or threadiness etc. such as carrying out processing at the high temperature of about 1000 DEG C can be enumerated.In addition, many potteries also can use as catalyst.
More particularly, the alkaline-earth metals oxide such as active carbon (high temperature particularly more than 500 DEG C carries out composing the active carbon of living), coke, activated charcoal, MgO, CaO, SrO, BaO can be used; La
2o
3, Th
2o
3etc. the oxide of group of the lanthanides, actinides; ZrO
2and TiO
2deng metal oxide; The metal carbonate of alkaline-earth metal etc.; SiO
2-MgO, SiO
2the composite oxides such as-CaO; By the zeolite of the alkali metal ions such as Rb or Cs or alkaline-earth metal ion-exchange; Add alkali metal compound or alkali earth metallic compound and generating portion or comprehensively poisoning FCC catalyst and FCC dead catalyst; Evaporation has the metal evaporation metal oxides such as alkali-metal Na/MgO, the K/MgO such as Na, K; KF/Al
2o
3, LiCO
3/ SiO
2deng alkali metal salt etc.Also their mixture and loaded article loaded article of supported solid (such as, on silica, coke etc.) etc. can be used.In addition, also preferably use once be heated as the mineral such as the dolomite of the mixture of MgO and CaO.
About their temperature programmed desorption of ammonia temperature (Ammoniatemperature-programmed temperatures), aluminium oxide is 50 ~ 250 DEG C, and silica gel is 30 ~ 200 DEG C, and zeolite is 200 ~ 600 DEG C, and active carbon is 0 ~ 100 DEG C.The FCC catalyst that Na is poisoning is 30 ~ 200 DEG C, and load has magnesian silica to be 0 ~ 60 DEG C, and load has magnesian active carbon to be 0 ~ 70 DEG C.Temperature programmed desorption of ammonia temperature, higher than the catalyst of 400 DEG C, is very strong acid catalyst, and its can by the bond fission between the carbon of the alkyl in grease, product is easily occurred degraded, and double bond between attack carbon, aromatic series is generated in a large number, thus adds the generation of coke.Therefore cause generate oil yield reduce, and then due to increase coke the activity of catalyst can be made to reduce faster, decarboxylation ability is reduced, thus the generation of carboxylic acid is increased, generate oil quality reduction, be therefore not preferred.If use temperature programmed desorption of ammonia temperature is higher than the catalyst of 400 DEG C, then the aromatic series owing to generating in oil is many, and Cetane number is low, and the content of acid is many, and the quality generating oil is low, is therefore in fact not suitable for using as diesel fuel.Be explained, in catalyst, when the catalyst using the temperature programmed desorption of ammonia such as active carbon, activated charcoal temperature below 100 DEG C, the mixture of grease and mineral oil can be used as raw material.This is because the catalyst such as active carbon, activated charcoal makes mineral oil degraded hardly.As mineral oil, reduced crude crude distillation obtained, the decompression light oil further for reduced crude decompression distillation obtained, decompression residuum, their hydrotreatment oil or pyrolysis oil and their mixture can be enumerated.In addition, the hydrocarbon that grease generates after decarboxylation is decomposed can also be used.These mineral oil are played a role as the extractant of the grease remained in residue, can raise the efficiency further.
If the heating-up temperature of grease decarboxylation decomposition catalyst is lower than 350 DEG C, then what can be observed decarboxylation decomposition reaction carries out slack-off, and causes the polymerizing curable of grease, thus makes the productivity ratio of hydrocarbon present the tendency of reduction.In addition, if higher than 475 DEG C, then the growing amount of the light gas and coke that can be observed carbon number less than 4 increases, and the growing amount of the product being principal component with the alkene of carbon number 8 ~ 24 and alkane presents the tendency of reduction, is therefore all not preferred.
As the reaction unit preparing biodiesel fuel, can using such as, possessing reaction vessel for receiving grease decarboxylation decomposition catalyst and by the reaction unit of the heater of the grease decarboxylation decomposition catalyst heating in reaction vessel.Reaction vessel can adopt fixed bed mode, thermopnore mode, rotary kiln mode, agitating mode etc.Wherein, preferred agitating mode.This be due to, once deteriorations such as reaction conditions in operation, the analyte (aromatic compound etc.) of grease etc. will be polymerized and be attached on the surface of grease decarboxylation decomposition catalyst, this polymer often makes multiple grease decarboxylation decomposition catalyst tie and is incorporated in caking in reaction vessel, thus can not operate, but adopt agitating mode just can carry out Mechanical Crushing, thus prevent caking.
In decarboxylation decomposition process, grease decarboxylation decomposition catalyst is heated, make catalyst arrive reaction temperature, then by spraying, injection, dropping, distribution etc., oil expression raw material or grease are imported in reaction vessel, thus make it contact with grease decarboxylation decomposition catalyst.Can process to continous way, also can process to batch-type.Grease with contacted by the grease decarboxylation decomposition catalyst heated and decompose, become imflammable gas and there is vapour pressure.By importing the flowing gas such as the inert gas such as nitrogen, helium or water vapour continuously or off and on, generated imflammable gas can be discharged to outside system.By the imflammable gas cooling of discharging, become biodiesel fuel oil.By being used as flowing gas by water vapour, making water-soluble composition be dissolved in water vapour, the effect of washing imflammable gas can be obtained, when using the catalyst such as CaO, can prevent the activity of following such catalyst from reducing.
The grease decarboxylation decomposition catalyst of inactivation also can as required, after it being taken out in reaction vessel or from reaction vessel, regenerate.
Present citing illustrates and the example that the grease contacted with grease decarboxylation decomposition catalyst reacts makes the CO of MgO (catalyst) and grease
2in conjunction with, grease is decomposed, forms magnesium carbonate.Magnesium carbonate is decomposed at 350 ~ 450 DEG C, causes decarboxylation, then the MgO after decarboxylation is recycled and reused for the decomposition of grease.
In addition, make CaO (catalyst) in the presence of moisture, with the CO of grease
2in conjunction with, grease is decomposed, forms calcium bicarbonate.Calcium bicarbonate is decomposed near 300 DEG C, causes decarboxylation, then the CaO after decarboxylation is recycled and reused for the decomposition of grease.
Pressure in reaction vessel, preferably can maintain atmospheric pressure and even malleation.This is because, decomposed by the decarboxylation of grease etc., generate the imflammable gas such as light oil or kerosene, once there is negative pressure, air will be made to enter in reaction vessel, the imflammable gas generated likely blast of fighting.
In decarboxylation decomposition process, as representing the liquid hourly space velocity (LHSV) of grease relative to the input amount (volume) of every 1 hour of grease decarboxylation decomposition catalyst (volume), being 0.05/h ~ 2.0/h, being preferably 0.3/h ~ 1.0/h.If liquid hourly space velocity (LHSV) is lower than 0.05/h, then treatment effeciency is low, and decomposed by 2 times, generation oil component can be made to become light gas, thus the yield of kerosene light oil composition is reduced, be therefore not preferred.In addition, if more than 2.0/h, then shorten the time of contact of catalyst and grease etc., grease resolution ratio reduces, and is therefore not preferred.
Invention according to claim 2 of the present invention, for the preparation method of biodiesel fuel according to claim 1, the method has following formation: above-mentioned grease decarboxylation decomposition catalyst and wantonly a kind or the both sides in above-mentioned grease are heated to 350 DEG C ~ 475 DEG C before there is decarboxylation decomposition reaction contacting.
According to this formation, except the effect obtained in claim 1, also obtain following effect.
(1) thermal medium is become by the grease decarboxylation decomposition catalyst that heats or by the side in the grease that heats or both sides, the temperature of the part that the surface of grease decarboxylation decomposition catalyst contacts with grease rises, due to the effect of grease decarboxylation decomposition catalyst, carry out the reacting balance that the ester bond part of glycerine is ftractureed.
Herein, when running starts, preferably by grease decarboxylation decomposition catalyst and grease both sides heating, the temperature in reaction vessel is kept evenly, react reposefully.After stable reaction, only to above-mentioned side's heating, energy consumption can be reduced like this.
Invention according to claim 3 of the present invention is the preparation method of the biodiesel fuel described in claim 1 or 2, wherein, uses oil expression raw material to replace above-mentioned grease.
According to this formation, except the effect that claim 1 or 2 obtains, also obtain following effect.
(1) if oil expression raw material contacts with grease decarboxylation decomposition catalyst at 350 DEG C ~ 475 DEG C, the celluloses such as the shell then extracted oil in raw material are carbonized, simultaneously, the lubricant component stripping of oil expression raw material, contact with grease decarboxylation decomposition catalyst, the ester bond part cracking of lubricant component, causes the de-CO shown in (changing 1)
2or de-CO reaction, can obtain the decomposition gas (hydrocarbon) becoming biodiesel fuel.
(2) extracting oil raw material owing to there is water vapour when being decomposed by heating, therefore, being suitable for using CaO etc. to have the grease decarboxylation decomposition catalyst of good function in the presence of moisture.
Herein, as oil expression raw material, the seed of the pulp of oil palm or seed, the endosperm of coconut, vegetable seed, the fruit of olive, purple perilla or castor-oil plant etc., the fruit before oil expression such as seed of manioca or wilson dogwood (Cornus wisoniana) or seed etc. can be used.In addition, the algae of some kind known, at intracellular deposits grease, also can use the concentrate that the dehydration of this algae is concentrated.Oil expression raw material is dry rear use preferably.Because moisture can be removed like this, improve the efficiency of heating surface.In addition, in order to utilize grease decarboxylation decomposition catalyst to improve decomposition efficiency, preferably use the oil expression raw material making its expanded surface area through pulverizing or fragmentation.Also the oil expression raw material after being squeezed out by oil by squeezing etc. can be used.Even if they are after oil expression, still residual a lot of greases, this is well-known.
Be explained, the cellulose of the shell of oil expression raw material etc., remains in due to charing in reaction vessel, therefore, is preferably taken out in reaction vessel by residual carbide as required.
As grease or oil expression raw material and the mixture of mineral oil, those oil expression raw materials etc. after carrying out hot pressed oil with mineral oil such as hexanes also can be used.Even if they are after oil expression, still residual a lot of greases, this is well-known.
In addition, the grease of the basic oil leftover bits and pieces of discharging from the refining step of grease or fish pomace, livestock products leftover bits and pieces (internal organ class) etc. or lipid are also a lot, can use as raw material.
In addition, above-mentioned grease decarboxylation decomposition catalyst can regenerate by being heated to 500 DEG C ~ 600 DEG C and being exposed in oxygen containing atmosphere.Can by one side causing its active grease decarboxylation decomposition catalyst reduced to heat by due to coke attachment etc., the coke adhered on the surface with burning-off grease decarboxylation decomposition catalyst of ventilating as much as possible regenerates, and is conducive to saving resource like this.
The regeneration of grease decarboxylation decomposition catalyst can directly be carried out in reaction vessel.The heating-up temperature of regeneration is preferably 500 DEG C ~ 600 DEG C.If lower than 500 DEG C, then regenerate needs and take a long time, impracticable.And if more than 600 DEG C, then can cause the sex change of grease decarboxylation decomposition catalyst due to the structure change of ceramic-like etc., thus likely causing active reduction, is therefore not preferred.
Although the organic acid contained in raw oil material or above-mentioned oil expression raw material can become catalyst poison and make the activity of catalyst reduce, this is the problem existed, but grease decarboxylation decomposition catalyst can easily make organic acid resolve into hydrocarbon and carbon dioxide, therefore, the problem that catalyst activity reduces not easily is produced.Therefore, even if part estimation activity reduced is interior, also there is no need to use catalyst in a large number, can not to rise owing to causing Appendage Tasks such as the process of used catalyst or reactivations operating cost or productivity ratio reduces.
Invention according to claim 4 of the present invention, for the preparation method of biodiesel fuel according to claim 3, the method has following formation: above-mentioned grease decarboxylation decomposition catalyst contains the carbon activated by heating under oxygen atmosphere, in above-mentioned reaction vessel by the carbide from oil expression raw material residual after preparing biodiesel fuel.
According to this formation, except the effect that claim 3 obtains, also can obtain following effect.
(1) by heating in oxygen atmosphere, the coke of the accumulation on surfaces of the grease decarboxylation catalyst in reaction vessel being burnt, thus grease decarboxylation decomposition catalyst is regenerated.
(2) cellulose of shell etc. of raw material of extracting oil remains in due to charing in reaction vessel, therefore, should take out aptly and discard, but the carbon due to it can be made to be transformed into activation, effectively can utilize as catalyst, so without the need to discarding.
(3) even do not carry out the region of industrialization or network of communication lines outfit, also grease decarboxylation decomposition catalyst can easily be prepared.
Herein, the activation from the carbide of oil expression raw material can directly be carried out in reaction vessel.The heating-up temperature of regeneration is preferably 500 DEG C ~ 600 DEG C.If lower than 500 DEG C, then the regeneration of catalyst and the activation of carbon need to take a long time, impracticable.And if more than 600 DEG C, then can cause the sex change of grease decarboxylation decomposition catalyst due to the structure change of ceramic-like etc., thus likely causing active reduction, is therefore not preferred.
Invention according to claim 5 of the present invention, for the preparation method of the biodiesel fuel described in wantonly 1 of Claims 1 to 4, the method has following formation: above-mentioned grease decarboxylation decomposition catalyst contains wantonly more than a kind in the mixture of carbon, activated charcoal, aluminium oxide, silica, magnesia, non-acid sexual type zeolite by alkali modification and their complex activated.
According to this formation, except the effect that Claims 1 to 4 obtains, also can obtain following effect.
(1) mixture of active carbon, activated charcoal, aluminium oxide, silica, magnesia, non-acid sexual type zeolite by alkali modification and their complex causes mineral oil degraded hardly, therefore, if the mixture of grease or oil expression raw material and mineral oil is used as raw material, then mineral oil can work as the extractant of grease residual in oil expression raw material or residue, can raise the efficiency further.
The preparation method of biodiesel fuel according to claim 6 of the present invention, for the preparation method of the biodiesel fuel described in wantonly 1 of Claims 1 to 5, the method has following formation: in above-mentioned decarboxylation decomposition reaction, and coexist molar ratio computing 1/10 ~ 10/1 (H
2o/ grease) water vapour.
According to this formation, except the effect that Claims 1 to 5 obtains, also can obtain following effect.
(1) because water vapour promotes the hydrolysis of ester bond, therefore, the decomposition efficiency of grease improves.
Herein, in the decarboxylation decomposition reaction of grease of the present invention, side reaction must generate water, and therefore, even if do not add water vapour in addition, reaction also can be carried out.Therefore, when the consumption of water vapour is mol ratio less than 1/10 time, its facilitation effect is not obvious.
If the moisture in raw material exceedes mol ratio 10/1, then the moisture generated in oil becomes many, then can cause quality and reduce, and therefore, must remove moisture (drying) in feed stage or from generation oil.When utilizing oil expression raw material or fish pomace, situation is suitable therewith.When following embodiment 6 uses soybean, as shown in table 3, why more moisture is is caused by this reason.But, as long as increase dewatered operation from generation oil at back segment, special problem would not be there is.
The preparation facilities of biodiesel fuel according to claim 7 of the present invention, the preparation facilities of the biodiesel fuel used in the preparation method for the biodiesel fuel described in wantonly 1 of claim 1 ~ 6, this device has following formation: have the 1st reaction vessel that an inside has above-mentioned grease decarboxylation decomposition catalyst, by the heating part of above-mentioned grease decarboxylation decomposition catalyst or above-mentioned grease or oil expression heating raw materials, oil expression raw material or grease are put into the throw-in part in above-mentioned 1st reaction vessel, and by the 1st gas leading-out portion that the admixture of gas of generation is derived from above-mentioned 1st reaction vessel.
According to this formation, following effect can be obtained.
(1) due to utilize by the grease decarboxylation decomposition catalyst that heats to while adding hot pressed oil raw material or grease, carry out decarboxylation decomposition reaction, therefore, the coke of generation etc. are little, and the thermal efficiency is high, carries out preparation of fuel with high yield.
(2) pass through raw oil material or oil expression heating raw materials and dropped into, can operate continuously, make the structure of reaction vessel become simple, thus be easy to management.
Herein, in the 1st reaction vessel, can agitating device be set.Particularly when using oil expression raw material, preferably agitating device is set, to make the catalyst in reaction vessel fully contact with oil expression raw material.
In decarboxylation decomposition process, grease decarboxylation decomposition catalyst is heated, make catalyst arrive reaction temperature, then by operations such as spraying, injection, dropping, distributions, oil expression raw material or grease are put in reaction vessel, thus make it contact with grease decarboxylation decomposition catalyst.The input of grease and oil expression raw material can be carried out to continous way, and also can carry out to batch-type.Grease contacts with the grease decarboxylation decomposition catalyst heated and decomposes, and becomes imflammable gas and has vapour pressure.By importing the flowing gas such as the inert gas such as nitrogen, helium or water vapour continuously or off and on, generated imflammable gas can be discharged to outside system.By the imflammable gas cooling of discharging, become biodiesel fuel oil.
The consumption of grease decarboxylation decomposition catalyst preferably adopts 5 more than volume %, more preferably adopts 20 more than volume %.If the consumption of grease decarboxylation decomposition catalyst is less than 5 volume %, then can reduce with the ratio of the grease of catalyst exposure, the ratio of the grease that thermal decomposition occurs owing to being heated be improved, thus the growing amount of light gas is increased, the yield generating oil reduces, and is therefore not preferred.In addition, when dropping into oil expression raw material, if more than 60 volume %, then when dropping into the large raw material of oil expression raw material equal-volume, not by with catalyst exposure and being increased by the raw material heated, and the discharge frequency of residue increases, and is therefore not preferred.
When dropping into oil expression raw material, it is further preferred that the consumption of grease decarboxylation decomposition catalyst adopts 50 below volume %.
When heat resolve will be carried out to oil expression raw material or grease, first make them arrive reaction temperature, then by operations such as spraying, injection, dropping, distributions, oil expression raw material or grease are put in reaction vessel, contact with grease decarboxylation decomposition catalyst to make it.Owing to utilizing warmed-up grease etc. to be heated by catalyst, therefore, can process continuously.When intermittently processing, considering the heat needed for heatable catalyst, preferably oil expression raw material or grease being heated to higher temperature, or by catalyst warm-up.
Invention according to claim 8 of the present invention, be the preparation facilities of biodiesel fuel according to claim 7, this device has following formation: possess one and to be connected with above-mentioned 1st gas leading-out portion and to be filled with the 2nd reaction vessel of above-mentioned grease decarboxylation decomposition catalyst, the generation admixture of gas of above-mentioned 1st reaction vessel to be imported to the 2nd gas leading-out portion that the gas introduction part of above-mentioned 2nd reaction vessel interior and decarboxylation is decomposed by the above-mentioned grease decarboxylation decomposition catalyst by above-mentioned 2nd reaction vessel admixture of gas derive.
According to this formation, except the effect that claim 7 obtains, also can obtain following effect.
(1) for importing the 2nd reaction vessel of the admixture of gas generated by the 1st reaction vessel, its inside is filled with above-mentioned grease decarboxylation decomposition catalyst, organic acid in the gas generated by the 1st reaction vessel is decarboxylation decomposition due to the effect of the grease decarboxylation decomposition catalyst of the 2nd reaction vessel, therefore, acid in product reduces further, thus quality is improved.
Organic acid contained in the organic acid generated in (2) the 1st reaction vessels or raw oil material, even if do not touch catalyst by the top of the 1st reactor, be exported together with the gas generated in the 1st reactor, also decarboxylation decomposition can be carried out in the 2nd reaction vessel, therefore the organic acid in product can be made to reduce, thus maintain high-quality.
(3), when causing the performance of catalyst to reduce when rotating device for a long time, the reaction in the 1st reaction vessel will become incomplete, and unreacted completely organic acid is mixed in generated admixture of gas, and the quality of product is reduced.But because device of the present invention can suppress the reduction of this quality, therefore, can longer time rotating device, thus improve running efficiency.
Herein, the 1st reaction vessel need not be identical with the grease decarboxylation decomposition catalyst used in the 2nd reaction vessel.In addition, owing to derive from the 1st reaction vessel and the admixture of gas imported in the 2nd reaction vessel is high temperature, therefore, need not heat to the grease decarboxylation decomposition catalyst of the 2nd reaction vessel.But, when the temperature of the grease decarboxylation decomposition catalyst of the 2nd reaction vessel in operating is reduced to below 350 DEG C, just need the heater being used for heating the grease decarboxylation decomposition catalyst of the 2nd reaction vessel.As the 2nd reaction vessel, the packed layer such as single hose or radial reactor reactor can be used.
Grease decarboxylation decomposition catalyst according to claim 9 of the present invention, the grease decarboxylation decomposition catalyst used in preparation facilities for the biodiesel fuel described in the preparation method of the biodiesel fuel described in wantonly 1 of claim 1 ~ 6 or claim 7 or 8, this catalyst has following formation: containing the solid acid catalyst by more than 1 in alkali metal and alkaline-earth metal kind having made sour point (acid point: refer to have acid point, reactivity is selected) poisoning.
According to this formation, following effect can be obtained.
(1) because acid point is weakened, therefore the double bond part in oil-control can rupture, thus can effectively cause decarboxylation to decompose.In addition, further suppress the generation of aliphatic acid.Therefore, the generation yield of fuel improves.
(2) inhibit the generation of coke, decrease the maintenance of device, and postpone the deterioration of catalyst.
Herein, it is poisoning that acid is put, and adopts more than 50%, more preferably adopts more than 90%.As the poisoning of tartaric acid point is less than 50%, then the generation of coke and light gas increases, and is not preferred.
By making acid point poisoning, temperature programmed desorption of ammonia temperature can be made to reduce.Adopt by poisoning and make the catalyst that temperature programmed desorption of ammonia temperature reduces, temperature programmed desorption of ammonia temperature is preferably lower than 400 DEG C, more preferably less than 200 DEG C, preferred lower than 100 DEG C further.If this is because, more than 400 DEG C, then easily make product become degraded, in addition, aromatic series generates in a large number, becomes coke, easily makes catalyst activity reduce.If lower than 100 DEG C, between carbon, key ruptures hardly, also can use for mixing the raw material having mineral wet goods.
Invention according to claim 10 of the present invention, be grease decarboxylation decomposition catalyst according to claim 9, this catalyst has following formation: above-mentioned solid acid catalyst contains FCC catalyst.
According to this formation, except the effect that claim 9 obtains, also can obtain following effect.
(1) due to can be used in oil fluid catalytic cracking in widely used FCC catalyst, therefore easily can obtain catalyst.
Herein, FCC catalyst refer to use in the fluid catalytic cracking flow process of oil, by the solid acid catalyst of the synthetic zeolite system of the grain powdery granulations of 40 ~ 80 μm.As the method making FCC catalyst poisoning with alkali metal, various method can be adopted, can adopt and in the aqueous solution of alkali metal salt, such as flood FCC catalyst to the method having made it poisoning.
In addition, as FCC catalyst, the FCC dead catalyst of industrial waste process also can be used as.FCC dead catalyst refers to the catalyst of discharging from the fluid catalytic cracking flow process of oil.In the fluid catalytic cracking flow process of oil, because coke laydown makes catalyst activity slowly reduce on catalyst surface.Therefore, the fluid catalytic cracking flow process of oil has by the operation making catalyst regeneration is burnt in the heating of this coke, and has in order to catalyst activity is kept certain and add the operation of raw catelyst and take out the operation of old catalyst.The old catalyst of this taking-up is FCC dead catalyst, most ofly processes as trade waste.FCC dead catalyst also has enough catalyst activities, can buy in addition with dog-cheap price.When coke makes catalyst function reduce at FCC dead catalyst deposited on silicon, as long as burnt the coke of catalyst surface by heatable catalyst in oxygen atmosphere, catalyst regeneration can be made.
Invention according to claim 11 of the present invention, for the preparation method of the biodiesel fuel described in wantonly 1 of claim 1 ~ 6, or the grease decarboxylation decomposition catalyst used in the preparation facilities of the biodiesel fuel described in claim 7 or 8, this catalyst has following formation: it is characterized in that containing: the carbon activated, activated charcoal, aluminium oxide, silica, non-acid sexual type zeolite by alkali modification, clay mineral, and in the mixture to be formed by their complex wantonly more than a kind by comprising the hydroxide of magnesium, oxide, the product that in carbonate, wantonly more than the a kind alkaline compound formed is coated with.
According to this formation, following effect can be obtained.
(1) by mixture that carbon with the activation by more than the a kind alkaline compound coating formed wantonly in the hydroxide of magnesium, oxide, carbonate, activated charcoal, aluminium oxide, silica, non-acid sexual type zeolite, clay mineral and the complex by them by alkali modification are formed, become degraded owing to making mineral oil hardly, therefore, if the mixture of grease or oil expression raw material and mineral oil is used as raw material, the extraction efficiency of grease just can be made to improve, thus the yield decomposing oil can be improved.
The effect of invention
As mentioned above, adopt the preparation method of biodiesel fuel of the present invention, following beneficial effect can be obtained.
Invention according to claim 1,
(1) a kind of like this preparation method of biodiesel fuel can be provided, different from FAME method in the past, the method does not need the alcohol of auxiliary material, therefore operating cost can be reduced significantly, and, the impurity such as the dienes in raw oil material or hydroxyl not easily remain in product, the growing amount of coke is few, also the not easily impurity such as by-product carboxylic acid (free fatty), therefore, can obtain in air etc., keep stable, black change and foreign odor not easily occur, biodiesel fuel that stability in storage is excellent, freezing point is about-20 DEG C mobility is also excellent.
(2) a kind of like this preparation method of biodiesel fuel can be provided, different from FAME method in the past, the method can not by-product glycerol, therefore, do not need the treatment technology of establishment glycerine and process man-hour etc., nor need to use adsorbent to adsorb the operation of the impurity such as removing peroxide, and then also not easily produce because coke separates out the caused problem such as catalyst activity reduction, catalyst agglomeration on the surface of the catalyst, thus stable operation can be carried out with high yield.
(3) can provide a kind of like this preparation method of biodiesel fuel, although there is free fatty in raw material, the method carries out de-CO by making the ester bond part of the glycerine of grease etc. ftracture
2reaction, the not easily impurity such as by-product carboxylic acid (free fatty), in reaction, the free fatty of by-product is also easily broken down into hydrocarbon and carbon dioxide, therefore, not easily produce the problem that catalyst activity that the carboxylic acid (free fatty) because of by-product causes reduces, even if part estimation activity reduced is interior, do not need to use catalyst in a large number yet, therefore, can not rise owing to causing Appendage Tasks such as the process of used catalyst or reactivations operating cost or productivity ratio reduces, production efficiency and productivity are all excellent.
(4) a kind of like this preparation method of biodiesel fuel can be provided, the method is not owing to needing the pretreatment etc. removing free fatty from raw oil material, and can react at ambient pressure, therefore, the preparation section of biodiesel fuel and reaction unit can be made to simplify, highly productive, can prepare biodiesel fuel with low cost simultaneously, thus can in the place construction of necessity for supplying the dispersed-type power sources feed system of the necessary energy.
(5) a kind of like this preparation method of biodiesel fuel can be provided, the method due to pyrolysis suppressed, therefore, yield becomes good, and meanwhile, the concentration of the aliphatic acid in product reduces, and product can be used as fuel relievedly.
(6) can by the preparation method that provide at a low price the biodiesel fuel of high-quality, due to catalyst stabilization keep active, therefore can reuse.
Invention according to claim 2, except the effect of claim 1, can also provide:
(1) a kind of preparation method of biodiesel fuel, the method make by the grease decarboxylation decomposition catalyst that heats or by the side in the grease that heats as thermal medium, the temperature of the part that the surface of grease decarboxylation decomposition catalyst is contacted with grease rises, the reacting balance utilizing the effect of grease decarboxylation decomposition catalyst that the ester bond part of glycerine is ftractureed carries out, therefore, the energy consumption for heating can be reduced.
(2) preparation method for biodiesel fuel, the temperature in reaction vessel, by heating grease decarboxylation decomposition catalyst and grease both sides when operating and starting, keeps evenly, thus carries out with making reacting balance by the method.
Invention according to claim 3, except the effect of claim 1 or 2, can also provide:
(1) a kind of preparation method of biodiesel fuel, in the method, when oil expression raw material contacts once at 350 DEG C ~ 475 DEG C with grease decarboxylation decomposition catalyst, the celluloses such as the shell in oil expression raw material will be carbonized, meanwhile, the lubricant component stripping of oil expression raw material, by contacting with grease decarboxylation decomposition catalyst, the ester bond part cracking of lubricant component, causes the de-CO shown in (changing 1)
2or de-CO, can obtain the decomposition gas (hydrocarbon) becoming biodiesel fuel, therefore, only need, by dry for the organic matter in a large number containing lubricant components such as oil expression raw materials, just to produce biodiesel raw material by raw material.
(2) preparation method of the biodiesel fuel that a kind of efficiency is higher, water vapour is produced due to during oil expression raw material decomposes, therefore, the method use those to resemble grease decarboxylation decomposition catalyst that CaO and so on can play function in the presence of moisture well, so comparatively preferred, in the case, oil expression raw material is used also can to prepare biodiesel raw material efficiently.
Invention according to claim 4, except the effect of claim 3, can also provide:
(1) a kind of preparation method of biodiesel fuel, coke on the surface of the grease decarboxylation catalyst be deposited in reaction vessel is burnt by heating in oxygen atmosphere by the method, thus grease decarboxylation catalyst is regenerated, therefore, catalyst can be reused.
(2) a kind of preparation method of biodiesel fuel, the celluloses such as the shell of original oil expression raw material can remain in reaction vessel due to charing, need to be suitable for taking out and discarding, but the present invention can be converted into the carbon activated, can catalyst be effectively it can be used as to utilize, owing to not needing to discard, thus can operate continuously.
(3) preparation method for biodiesel fuel, even the method is not having industrialized region, also can prepare the grease decarboxylation decomposition catalyst that can operate continuously, and therefore, no matter what region all easily introduces the present invention.
Invention according to claim 5, except the effect of Claims 1 to 4, can also provide:
(1) a kind of preparation method of biodiesel fuel, because the mixture of active carbon, activated charcoal, aluminium oxide, silica, magnesia, non-acid sexual type zeolite by alkali modification and their complex makes mineral oil become degraded hardly, therefore, the mixture of grease or oil expression raw material and mineral oil uses as raw material by the present invention, like this, mineral oil just works as the extractant of grease, thus reaches high efficiency.
Invention according to claim 6, except the effect of Claims 1 to 5, can also provide:
(1) preparation method for biodiesel fuel, the method utilizes water vapour to promote the hydrolysis of ester bond, therefore improves the decomposition efficiency of grease.
Invention according to claim 7, can provide:
(1) preparation facilities for biodiesel fuel, this device can make oil expression raw material or grease contact with grease decarboxylation decomposition catalyst at 350 DEG C ~ 475 DEG C and to carry out decarboxylation decomposition reaction simultaneously, and therefore, the output of coke etc. is few, and the thermal efficiency is high, and yield is high.
(2) preparation facilities for biodiesel fuel, this device passes through raw oil material or oil expression heating raw materials and is dropped into, and easily, the thermal efficiency is high in running continuously, is easy to manage.
Invention according to claim 8, except the effect of claim 7, can also provide:
(1) a kind of preparation facilities of biodiesel fuel, in this device, the 2nd reaction vessel for importing the admixture of gas that the 1st reaction generates is filled with above-mentioned grease decarboxylation decomposition catalyst therein, organic acid in the gas that 1st reaction vessel generates carries out decarboxylation decomposition under the effect of the grease decarboxylation decomposition catalyst of the 2nd reaction vessel, therefore, acid in product reduces further, makes to generate the best in quality of oil.
(2) a kind of preparation facilities of biodiesel fuel, even if organic acid contained in the organic acid that this device generates in its 1st reaction vessel or raw oil material is by the top of the 1st reactor, be not exported together with the gas generated in the 1st reactor with catalyst exposure, also can be decomposed by decarboxylation in the 2nd reactor, therefore, organic acid in product reduces, thus can maintain the high-quality generating oil.
(3) preparation facilities for biodiesel fuel, when causing the performance of catalyst to reduce when device long time running, the reaction in the 1st reaction vessel becomes incomplete, and the organic acid in the admixture of gas generated increases, and the quality generating oil reduces.But this device can suppress the reduction generating oil quality, can make the running of device longer time, therefore running efficiency is high.
Invention according to claim 9, can provide:
(1) a grease decarboxylation decomposition catalyst, by making acid point weaken, the double bond part in oil-control can rupture, thus decarboxylation decomposition can occur effectively.In addition, also inhibits organic acid to generate.Therefore, the generation yield of fuel is high.
(2) a grease decarboxylation decomposition catalyst, this catalyst can suppress the generation of coke, can reduce the maintenance of device, and the deterioration of deferrable catalyst.
Invention according to claim 10, except the effect of claim 9, can also provide:
(1) a grease decarboxylation decomposition catalyst, owing to can utilize with shirtsleeve operation the FCC catalyst be widely used, therefore makes enforcement become easy.And, even if the catalyst performance of FCC catalyst reduces, also can regenerate simply, therefore, not need very large-scale regenerating unit.In addition, do not need, by carrying out the processing method processed again from birth, therefore to carry out the running of equipment relievedly owing to establishing.
(2) a grease decarboxylation decomposition catalyst, owing to also can utilize by the FCC dead catalyst as offal treatment, therefore can make operating cost very low.
Invention according to claim 11, can provide:
(1) a kind of grease decarboxylation decomposition catalyst, this catalyst is by the hydroxide by magnesium, oxide, the carbon of the activation of wantonly more than the a kind alkaline compound coating formed in carbonate, activated charcoal, aluminium oxide, silica, non-acid sexual type zeolite by alkali modification, clay mineral, and the mixture to be formed by their compound, because mineral oil almost can not be become degraded by this catalyst, therefore, when the mixture of grease or oil expression raw material and mineral oil is used as raw material, the extraction efficiency of grease can be made to improve, the yield decomposing oil is high.
[accompanying drawing explanation]
Fig. 1 is the structure chart of the reaction unit of embodiment 1
Fig. 2 is the structure chart of the reaction unit of embodiment 2
Fig. 3 is the structure chart of the reaction unit of embodiment 3
Fig. 4 is the figure of the carbon number distribution that the decomposition oil obtained in embodiment 2 is shown
Fig. 5 is the figure of the carbon number distribution that the decomposition oil obtained in embodiment 7 is shown
Fig. 6 is the figure of the carbon number distribution that the decomposition oil obtained in embodiment 8 is shown
Fig. 7 is the figure of the carbon number distribution that the decomposition oil obtained in embodiment 9 is shown
Fig. 8 is the figure of the carbon number distribution that the decomposition oil obtained in embodiment 10 is shown
[detailed description of the invention]
Below, the present invention is specifically described by embodiment.Be explained, the present invention is not limited to these embodiments.
(embodiment 1)
First the reaction unit used in embodiment 1 ~ 7 and embodiment 9 ~ 14 is described.
Fig. 1 is the structure chart of the reaction unit of embodiment 1.
In figure, 1 is the reaction unit of the embodiment 1 used in embodiments of the invention; 2 is reaction vessel; 3 be the silica of the granular of storage in reaction vessel 2, the carbon activated, solid base, the grease decarboxylation decomposition catalyst such as poisoning FCC catalyst; 4 is the heater for the catalyst 3 of storage in reaction vessel 2 being heated to 350 ~ 475 DEG C; 5 is the raw material throw-in part for being dropped into grease or oil expression raw material in reaction vessel 2 by operations such as spraying, dropping, distributions; 6 is the flowing gas introduction part for importing the flowing gas such as inert gas or water vapour such as nitrogen in reaction vessel 2; 7 is the agitating device for stirring catalyst 3; 8 for for by the product generated in reaction vessel 2 along with flowing gas exports to the first delivery line outside reaction vessel 2 together; 9 for being connected with the first delivery line 8, for storing the decomposition oil reservoir of the decomposition product (hereinafter referred to as decomposing oil) that product mid-boiling point is the temperature of 0 DEG C ~ reaction vessel; 10 is the discharge pipe that one end is connected with the oily reservoir 9 of decomposition; 11 for be disposed on discharge pipe 10, for discharge pipe 10 being cooled to 0 DEG C and making the cooling tube of the decomposition oil liquify in product; 12 for be connected with the other end of discharge pipe 10, for store be cooled to-80 DEG C, the cold-trap device of decomposition product (hereinafter referred to as light oil) that its boiling point has been the liquefaction of-80 ~ 0 DEG C; 13 is the gas outlet pipe that one end is connected with cold-trap device 12.
(embodiment 2)
Secondly the reaction unit of the embodiment 2 used in embodiment 8 is described.
Fig. 2 is the structure chart of the reaction unit of this embodiment 2.
In figure, 21 is the reaction unit of embodiment 2.For the part common with Fig. 1, adopt identical symbol and omit the description.22 is the heating part for heating raw grease or oil expression raw material.23 for when operate start time etc. the temperature of catalyst 3 low auxiliary heating portion for heating.
(embodiment 3)
Secondly the reaction unit of the embodiment 3 used in embodiment 15 is described.
Fig. 3 is the structure chart of the reaction unit of this embodiment 3.
In figure, 31 is the reaction unit of embodiment 3.For the part common with Fig. 1, adopt identical symbol and omit the description.Be explained, 32 is the 1st reaction vessel of embodiment 3, suitable with the reaction vessel 2 of Fig. 1.33 is the grease decarboxylation catalyst A such as the granular silica of storage in the 1st reaction vessel 32; 8 for for by the product generated in the 1st reaction vessel 32 along with flowing gas exports to the 1st delivery line outside the 1st reaction vessel 32 together; 34 is the 2nd reaction vessel; 35 is the grease decarboxylation decomposition catalyst B such as granular silica, the carbon activated, solid base received in the 2nd reaction vessel 34; 38 the 2nd delivery lines of deriving for the gas for decarboxylation in the 2nd reaction vessel 34 has been decomposed.
Embodiment 1
As grease decarboxylation decomposition catalyst (hereinafter referred to as catalyst) 3, use catalyst with silica (Tomita scholar シ リ シ ア KCC system, trade name: キ ヤ リ ア Network ト Q-15, particle diameter 1.18 ~ 2.36mm), this catalyst 50mL is accommodated in the reaction vessel 2 of volume 150mL, while stir with agitating device 7 (50rpm), be heated to 420 DEG C.The heating-up temperature of catalyst 3 to contact with catalyst 3 measure by making to be contained in not shown thermocouple in reaction vessel 2.
After confirming that the temperature of catalyst 3 has risen to 420 DEG C of reaction temperature, palm oil (grease) is put in the reaction vessel 2 atmospheric pressure from raw material throw-in part 5 by dropping.The input amount of grease is 0.25mL/ minute, is 50mL/ minute from the import volume of the flowing gas (nitrogen) of flowing gas introduction part 6 importing.
By dropping into the grease adding up to 75g, obtain product.To decomposing the decomposition oil of oily reservoir 9 storage and analyzing from the composition of the gaseous matter (carbon monoxide, carbon dioxide and light hydrocarbon gas) of gas outlet pipe 13 discharge.The analysis of decomposing oil uses GC-MS to carry out, and the analysis of the carbon monoxide in gaseous matter, carbon dioxide uses GC-TCD to carry out, and the analysis of light hydrocarbon gas uses GC-FID to carry out.In addition, the catalyst TG-DTA after experiment analyzes.
Embodiment 2
Make the catalyst of the silicon dioxide carried MgO of catalyst used in embodiment 1, make reaction temperature be 410 DEG C, in addition, carry out similarly to Example 1.
Be explained, make the preparation method of the catalyst of silicon dioxide carried MgO as follows: relative to the catalyst silica used in embodiment 1, use content to be equivalent to the magnesium nitrate (Mg (NO of magnesium metal 10 quality %
3)
26H
2o) the aqueous solution, adopts Incipient Wetness method to make silica be impregnated in this aqueous solution, after dipping, dry at 120 DEG C, then at 500 DEG C, in an atmosphere roasting 3 hours.
Embodiment 3
As grease decarboxylation decomposition catalyst, use activated charcoal (particle diameter after Mitsui Mining Co Ltd. BJ Offc's system, fragmentation is 1.18 ~ 2.36mm), make reaction temperature be 400 DEG C, in addition, carry out similarly to Example 1.
Embodiment 4
Make the catalyst of the activated charcoal load MgO used in embodiment 3, make reaction temperature be 400 DEG C, in addition, carry out similarly to Example 1.
Be explained, make the preparation method of the catalyst of activated charcoal load MgO as follows: relative to the activated charcoal used in embodiment 3, use content to be equivalent to the magnesium nitrate (Mg (NO of magnesium metal 10 quality %
3)
26H
2o) the aqueous solution, adopts Incipient Wetness method to make activated charcoal be impregnated in this aqueous solution, after dipping, dry at 120 DEG C, then 350 DEG C, roasting 3 hours in blanket of nitrogen.
(comparative example 1)
As catalyst, use FCC dead catalyst, make reaction temperature be 420 DEG C, in addition, carry out similarly to Example 1.
Be explained, FCC dead catalyst be by by use in fluid catalytic cracking (the FCC:fluid catalyst cracking) flow process of oil, the catalyst of the solid acid catalyst regeneration of the synthetic zeolite system that is a granulated into the grain powdery of 40 ~ 80 μm.
The analysis result of the product in above embodiment and comparative example is described.
Table 1 illustrates the yield of the amount Sum decomposition oil of product in embodiment 1 ~ 4 and comparative example 1.
[table 1]
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | |
| Input amount (g) | 75.0 | 75.0 | 75.0 | 75.0 | 75.0 |
| Decompose oil (g) | 45.2 | 47.7 | 42.8 | 38.0 | 34.2 |
| Light oil (g) | 0.0 | 1.9 | 1.7 | 1.7 | 3.7 |
| C1 ~ C4 gas (g) | 8.8 | 5.3 | 3.8 | 3.8 | 9.1 |
| CO、CO 2(g) | 2.3 | 3.4 | 3.6 | 4.0 | 2.8 |
| Residue (g) | 7.2 | 9.2 | 5.4 | 5.7 | 15.0 |
| Water composition (g) | 2.4 | 2.0 | 1.8 | 1.4 | 4.0 |
| Decompose oily yield (%) | 60.3 | 63.7 | 57.1 | 50.7 | 45.6 |
As can be seen from Table 1, the decomposition oil yield of embodiment 1 ~ 4 is more than 50%, and comparative example 1 is 46%.About residue, embodiment 1 ~ 4 is less than comparative example 1.Therefore, this residue is inquired into.
Catalyst TG-DTA analysis result after experiment, the catalyst of embodiment 1 ~ 4 remains the coke of about 9%, and on the catalyst (FCC dead catalyst) of comparative example 1, remains the coke of about 30%.In addition, as can be seen from the GC-MS analysis result decomposing oil, about 50% alkane, about 20% alkene, about 20% aromatic compound is there is in the decomposition oil of comparative example 1, and in the decomposition oil of embodiment 1 ~ 4, there are about 50 ~ 60% alkanes, about 30 ~ 40% alkene, but there is aromatic compound hardly.Can infer from this result, residue is coke mainly, and coke is the polymer of the aromatic compound from alkene generated due to the effect of the acid point of catalyst (FCC dead catalyst).In embodiment 1 ~ 4, owing to using neutral silica or solid base as catalyst, generate aromatic compound hardly, therefore can infer, the generation of coke is also few, and the growing amount of residue is also few.
In addition, in comparative example 1, decomposing in oil a small amount of alcohol and aliphatic acid that detect as oxygen carrier, and in embodiment 1 ~ 4, do not detecting these materials, mainly generating ketone.The decomposition oil of comparative example 1 produces foreign odor, places about 1 week, can the blackening of visual confirmation major part, and the decomposition oil of embodiment 1 ~ 4 neither blackening there is not foreign odor yet, stability in storage is excellent.Infer that its reason is the impact of the impurity such as carboxylic acid (aliphatic acid) contained in decomposition oil due to comparative example 1.。
Fig. 4 is the figure of the result carbon number distribution that the decomposition oil that embodiment 2 obtains is shown.On the other hand, the aliphatic acid composition of the grease (palm oil) used in experiment, laurate (C12) is 0.2%, myristic acid (C14) is 1.1%, palmitic acid (C16) is 44.0%, and stearic acid (C18) is 4.5%, and oleic acid (C18:1) is 39.2%, linoleic acid (C18:2) is 10.1%, and leukotrienes (C18:3) is 0.4%.As can be seen from Figure 4, in embodiment 2, main alkane or the alkene generating the carbon number corresponding with the aliphatic acid contained by grease.Other embodiments also have same tendency.
Measure the pour point of the decomposition oil obtained according to 11SK2269 (pour point of crude oil and petroleum product and petroleum product cloud test method), be-12.5 DEG C.Can find out, the pour point of commercially available general light oil is-7 DEG C, therefore, can prepare as the decomposition oil of the low like that pour point of light oil.
Table 2 shows the carbon monoxide of gaseous matter and the amount of carbon dioxide that generate in embodiment 1 ~ 4 and comparative example 1.
Find out after comparing, amount of carbon dioxide increases according to the order of comparative example 1, embodiment 1, embodiment 2 ~ 4.The catalyst of comparative example 1 is solid acid, the catalyst of embodiment 1 is silica (neutrality), and the catalyst of embodiment 2 ~ 4 is solid base, therefore can confirm, by as embodiment 1 ~ 4 using silica or solid base as catalyst, optionally can reclaim CO
2.
Can infer that the decomposition mechanism of grease is as follows from the result of table 2 and Fig. 4.The grease contacted with by the grease decarboxylation decomposition catalyst heated, except generating glycerine, also generates aliphatic acid.The carboxy moiety of the aliphatic acid generated is as CO
2be removed, the carbochain stayed is recovered as decomposition oil.Glyceryl reclaims as light hydrocarbon gas such as propane.
[table 2]
| CO(mol) | CO 2(mol) | |
| Embodiment 1 | 0.011 | 0.045 |
| Embodiment 2 | 0.007 | 0.074 |
| Embodiment 3 | 0.009 | 0.076 |
| Embodiment 4 | 0.006 | 0.086 |
| Comparative example 1 | 0.010 | 0.025 |
As can be seen from above embodiment, because the growing amount of coke is few, also the not easily impurity such as by-product carboxylic acid (free fatty), therefore, obtain stable to air etc., not easily there is black change or foreign odor, stability in storage is excellent, pour point is low, mobility is excellent biodiesel fuel.
Be explained, in embodiment 3, even if when using the carbon of activation to replace the activated charcoal as catalyst, also obtain same result.
Embodiment 5
Be used in the catalyst (catalyst similarly to Example 2) of catalyst supported on silica MgO, by (0.25mL/ minute) in fact putting under atmospheric pressure reaction vessel by dropping with the waste edible oil (soybean oil mixes 75g with rapeseed oil) crossed in 1 week in university dining room, simultaneously, as flowing gas, use He gas (50mL/ minute), in addition, carry out similarly to Example 1.
Embodiment 6
Use commercially available soybean (dry soybean, is produced from Hokkaido) as oil expression raw material, carry out the experiment of decomposing oil from the preparation of oil expression raw material.Because soybean is easily decomposed, soybean particle is broken into the size being approximately its half.Be used in the catalyst (catalyst similarly to Example 2) of catalyst supported on silica MgO, reaction temperature is made to be 410 DEG C, with large feeder (マ イ Network ロ Off イ mono-ダ), the broken thing (500g) of soybean is put in the reaction vessel under atmospheric pressure bit by bit, in addition, carry out similarly to Example 1.
Embodiment 7
Use the rice bran of discharging from rice-hulling mill as raw oil material, carry out the experiment of decomposing oil from the preparation of oil expression raw material.Be used in the catalyst (catalyst similarly to Example 2) of catalyst supported on silica MgO, reaction temperature is made to be 410 DEG C, with large feeder, rice bran (500g) is bit by bit put in the reaction vessel under atmospheric pressure, in addition, carry out similarly to Example 1.
Embodiment 8
As raw oil material, use the very many and curcas oil that decomposition oil recovery rate when adopting previous methods process is very low of unrighted acid as raw oil material, use the reaction unit of embodiment 2, be prepared and decompose oily experiment.
As grease decarboxylation decomposition catalyst 3, use the catalyst at catalyst supported on silica MgO identical with embodiment 2.This catalyst 50mL is encased in the reaction vessel 2 of volume 150mL.Raw oil material heating part 22 is heated to 450 DEG C.The heating-up temperature of raw oil material, to contact with raw oil material measure by making to put into not shown thermocouple in heating part 22.
Confirm that the reaction temperature of raw oil material rises to 450 DEG C, from raw material throw-in part 5 curcas oil (grease) put into by dropping in the reaction vessel 2 atmospheric pressure.The input amount of grease is 1.0mL/ minute, and the import volume from the flowing gas (nitrogen) of flowing gas introduction part 6 is 50mL/ minute.
By dropping into the grease adding up to 75g, obtain product.
Embodiment 9
Use animal fat as raw material, be prepared the experiment of decomposing oil.As raw oil material, the fat (500g) of the pig of meat-packing plant being discharged is heated to 80 DEG C and becomes liquid state to use, and in addition, carries out similarly to Example 4.
Embodiment 10
As raw oil material, the fat (500g) of the ox of meat-packing plant being discharged is heated to 80 DEG C and becomes liquid state to use, and in addition, carries out similarly to Example 4.
Table 3 illustrates the amount of the product in embodiment 5 and embodiment 6, embodiment 8 and the yield decomposing oil.
Be explained, in embodiment 6, decompose in oil, oil components, water composition, sediment, floating material are mixed in together.Can think, this is because oil expression raw material contains the cause of the composition beyond abundant grease.Therefore, the decomposition oil yield of embodiment 6, owing to needing the impact of deducting sediment etc., therefore, different from embodiment 1 ~ 5, embodiment 6 converts according to the ratio of oil components relative to input amount.In addition, in embodiment 6, do not carry out the analysis of gaseous matter.This be due to grease beyond the large cause of the impact of composition.
When using oil expression raw material in raw material in washy situation, because the water composition resembled in the decomposition oil that generates embodiment 6 increases, in order to use as fuel, need from raw material or from decomposition oil dewatered operation.
[table 3]
| Embodiment 5 | Embodiment 6 | Embodiment 8 | |
| Input amount (g) | 75.0 | 500.0 | 75.0 |
| Decompose oil (g) | 46.1 | - | 47.3 |
| Light oil (g) | 3.3 | 12.8 | 3.3 |
| C1-C4 gas (g) | 3.3 | - | 5.4 |
| CO、CO 2(g) | 4.5 | - | 5.7 |
| Residue (g) | 7.4 | 282.9 | 8.9 |
| Water composition (g) | 1.8 | 101.6 | 0.6 |
| Decompose oily yield (%) | 61.5 | 5.7 | 63.1 |
In table 3, as described in Example 5, confirm also to obtain with the yield of more than 60% decomposing oil from waste edible oil.This result substantially same with the embodiment 1 ~ 4 using palm oil as raw oil material.Consider that waste edible oil is compared with palm oil, the degree of oxidation is remarkable, but can be found out by the present embodiment, can obtain decomposing oil with high yield.
In addition, as described in Example 6, confirm also to obtain oil component with the yield of 5.7% from oil expression raw material (soybean).Because the grease containing ratio in Japanese domestic soybean is about 10wt%, therefore the yield 5.7wt% of oil component can be described as quite high yield.
Fig. 5 illustrates the carbon number distribution of the decomposition oil obtained from rice bran in embodiment 7.Can observe, generate the hydrocarbon of the wide region carbon number of C5 ~ C34.Kerosene light oil composition particularly containing a lot of carbon number C10 ~ C20.In addition, the aromatic hydrocarbon containing the 20%C6 ~ C13 that has an appointment in oil is decomposed.In rice bran, lipase is many, and free fatty is many, but oxidizability (oxidation degree) is 0.35mgKOH/g, oxidation permanence (oxidation stability) is more than 24h, can use fully as biodiesel fuel.
From the result that curcas oil obtains in embodiment 8 shown in table 3.Curcas oil contains palmitic acid (C16) 14.9%, stearic acid (C18) 6.9%, oleic acid (C18:1) 41.8%, linoleic acid (C18:2) 34.8%, because the ratio of unrighted acid is high, therefore adopt the yield of pyrolysismethod low, but adopt method of the present invention, demonstrating high decomposition oil recovery rate, is 63.1%.Fig. 6 illustrates the carbon number distribution of the hydrocarbon in the decomposition oil obtained.Result demonstrates, and carbon number is in the distribution of wide scope, and double bond is saved.
And then the phosphorus acid content of curcas oil is high, if employing method is in the past by its turning sludge into fuel, then phosphoric acid remains in fuel oil, occurs the problem damaging engine etc.When adopt IPC method measure embodiment 8 decomposition oil and as phosphoric acid concentration in the curcas oil of raw oil material time, the phosphoric acid concentration in raw oil material is about 10mg/L, and in contrast, the phosphoric acid concentration decomposed in oil only has 0.9mg/L.This just shows, the phosphoric acid in raw oil material can not be transferred to and decompose in oil, can obtain the decomposition oil that phosphorus acid content is low.
From the carbon number distribution of the hydrocarbon the decomposition oil that lard obtains in embodiment 9 shown in Fig. 7, from the carbon number distribution of the hydrocarbon the decomposition oil that butter obtain in embodiment 10 shown in Fig. 8.Generate the hydrocarbon of the wide region carbon number of C5 ~ C34 from lard, generate the hydrocarbon of the wide region carbon number of C5 ~ C31 from butter.The kerosene light oil composition decomposed in oil is all about 65%.
Can be found out by above embodiment, easily can gather oil component from waste edible oil or oil expression raw material, animal fat.The preparation method of biodiesel fuel of the present invention, can not by-product glycerol owing to not needing alcohol (auxiliary material), and therefore, serviceability is high.
Embodiment 11
Use the catalyst having made the FCC dead catalyst of use in comparative example 1 poisoning with NaCl, in addition, carry out in the same manner as comparative example 1.
Be explained, the preparation method of the catalyst having made FCC dead catalyst poisoning with NaCl is, relative to FCC dead catalyst 50g, adds the NaCl aqueous solution 1.0L of 50g/L, within 1 hour, makes 50 DEG C ± 5 DEG C process.The acid point of the catalyst that the method obtains is nearly 90% poisoning.When adopting temperature programmed desorption of ammonia method to evaluate the acid point of the catalyst that the method obtains, the acid point of nearly 90% is poisoning.
Embodiment 12a
Except using the silica belonging to solid acid catalyst as except catalyst, all the other carry out in the same manner as comparative example 1.
Embodiment 12b
Using the catalyst by having made with magnesium nitrate aqueous solution the silica that uses in embodiment 12a poisoning, in addition, carrying out in the same manner as comparative example 1.
Be explained, utilize magnesium nitrate aqueous solution to be, relative to silica 50g, add the Mg (NO of 50g/L to the preparation method of the catalyst having made silica poisoning
3)
2aqueous solution 1.0L, makes 50 DEG C ± 5 DEG C process for 1 hour.When adopting temperature programmed desorption of ammonia method to evaluate the acid point of the catalyst that the method obtains, the acid point of nearly 90% is poisoning.
Embodiment 13
Using by making with Mg the FCC dead catalyst that uses in comparative example 1 poisoning and then make the catalyst of its supported magnesium oxide, in addition, carrying out in the same manner as comparative example 1.
Be explained, utilize Mg to make FCC dead catalyst poisoning and then make the preparation method of the catalyst of its supported magnesium oxide be, relative to FCC dead catalyst 50g, add the Mg (NO of 50g/L
3)
2aqueous solution 1.0L, makes 50 DEG C ± 5 DEG C process for 1 hour.Herein, load refers to that magnesian amount contained on a catalyst reaches the state that can make more than the poisoning aequum of acid point.
[table 4]
| Embodiment 11 | Embodiment 12b | Embodiment 13 | Comparative example 1 | Embodiment 12a | |
| Input amount (g) | 75.0 | 75.0 | 75.0 | 75.0 | 75.0 |
| Decompose oil (g) | 39.3 | 53.8 | 48.2 | 34.2 | 40.2 |
| Light oil (g) | 5.0 | 1.8 | 4.7 | 3.7 | 2.8 |
| C1-C4 gas (g) | 9.3 | 5.4 | 5.2 | 9.1 | 7.3 |
| CO、CO 2(g) | 2.6 | 11.8 | 9.5 | 2.8 | 6.6 |
| Residue (g) | 14.6 | 11.3 | 12.0 | 15.0 | 13.3 |
| Water composition (g) | 3.6 | 0.3 | 0.5 | 4.0 | 3.0 |
| Decompose oily yield (%) | 52.3 | 71.8 | 55.6 | 45.6 | 50.2 |
| The segmentation of residue | Embodiment 11 | Embodiment 12b | Embodiment 13 | Comparative example 1 | Embodiment 12a |
| Coke (g) | 3.5 | 3.2 | 3.1 | 11.7 | 8.2 |
| Higher boiling oil component (g) | 11.1 | 8.1 | 8.9 | 3.3 | 5.1 |
Table 4 illustrates the result of the situation having made acid point poisoning.The top of this table illustrates the yield of the amount Sum decomposition oil of the product in comparative example 1, embodiment 11, embodiment 12a, embodiment 12b and embodiment 13.
Utilizing alkali to make, solid acid catalyst is poisoning increases CO
2generation, and improve decompose oil yield.And then by making its supported magnesium oxide increase CO
2generation and improve decompose oil yield.While raising yield, reduce the amount of residue.The bottom of table 4 illustrates the segmentation of this residue.Due to by making solid acid catalyst become alkalosis, the fracture of the double bond part in grease can be reduced, therefore can think, compare with 2 with comparative example 1, the fixed acid catalyst of alkalosis can make the amount of the coke of by-product significantly reduce, and the yield decomposing oil improves.
Embodiment 14
Except making reaction temperature be except 350 DEG C, all the other carry out similarly to Example 2.
Embodiment 15
Except making reaction temperature be except 475 DEG C, all the other carry out similarly to Example 2.
(comparative example 2)
Except making reaction temperature be except 300 DEG C, all the other carry out similarly to Example 2.
(comparative example 3)
Except making reaction temperature be except 550 DEG C, all the other carry out similarly to Example 2.
[table 5]
| Comparative example 2 | Embodiment 14 | Embodiment 2 | Embodiment 15 | Comparative example 3 | |
| Reaction temperature (DEG C) | 300 | 350 | 410 | 475 | 550 |
| C1-C4 gas (%) | 12.4 | 7.2 | 7.1 | 12.1 | 35.7 |
| Level of residue (%) | 35.2 | 16.3 | 12.3 | 15.5 | 20.7 |
| Decompose oily yield (%) | 30.3 | 55.8 | 63.7 | 60.4 | 35.5 |
Table 5, for illustrating the table of each temperature on the impact of the oily yield of decomposition, shows the yield of the amount Sum decomposition oil of product in comparative example 2, embodiment 14, embodiment 2, embodiment 15 and comparative example 3.
Demonstrate thus, the temperature range of reaction is preferably 350 DEG C ~ 475 DEG C.At 300 DEG C (comparative examples 2), delay of response, impracticable.Also can think in addition, owing to causing the polymerizing curable of grease, level of residue be increased, the productivity ratio of hydrocarbon reduces.At 550 DEG C (comparative examples 3), the yield decomposing oil is low, and level of residue is many, therefore can think and cause pyrolysis, and the growing amount of gas and coke increases.
(comparative example 4)
Through repeatedly reaction repeated, the activity of catalyst slowly reduces.Except the catalyst reduced except using this activity, all the other carry out similarly to Example 2.When the carbon containing ratio of the catalyst this activity reduced measures as the heating loss heated 1 hour at 800 DEG C in air atmosphere, its value is 45 % by weight.
Embodiment 16
In the reaction vessel adding the catalyst used in comparative example 4, make the mist of air 50%+ nitrogen 50% with the traffic flow of 200ml/ minute, while catalyst be heated to 500 DEG C ± 20 DEG C and keep 6 hours.Then, carbon content is measured in the same manner as comparative example 4.In regenerative operation, paddle is rotated with the rotating speed of 10 beats/min, slowly stirs.Secondly, except using the catalyst of regeneration, all the other carry out similarly to Example 2.
Embodiment 17
Except maintenance temperature when making regeneration is that except 550 DEG C ± 20 DEG C, all the other carry out similarly to Example 16.
Embodiment 18
Except maintenance temperature when making regeneration is that except 600 DEG C ± 20 DEG C, all the other carry out similarly to Example 16.
(comparative example 5)
The heating of catalyst during except making regeneration keeps temperature to be that except 450 DEG C ± 20 DEG C, all the other carry out similarly to Example 16.
(comparative example 6)
The heating of catalyst during except making regeneration keeps temperature to be that except 650 DEG C ± 20 DEG C, all the other carry out in the same manner as embodiment 12b.
[table 6]
The table of the impact that table 6 is regeneration and regeneration temperature that catalyst is shown, the result of embodiment 2 shown in it and comparative example 4 ~ 6, embodiment 16 ~ 18.Illustrate thus, by oxygen containing atmosphere, remain on 500 DEG C ~ 600 DEG C, can catalyst regeneration be made.In 450 DEG C (comparative example 4) regeneration slowly, carbon remains, active reduction.Also demonstrate in addition, at 650 DEG C, causing active reduction, is not preferred.The catalyst (embodiment 16-18) of regeneration demonstrates the decomposition oil recovery rate more taller than raw catelyst (embodiment 2), can think, this is the catalyst role owing to causing acid point to weaken by using.
Embodiment 19
Except making liquid hourly space velocity (LHSV) be except 0.05/h, all the other carry out similarly to Example 2.
Embodiment 20
Except making liquid hourly space velocity (LHSV) be except 2.0/h, all the other carry out similarly to Example 2.
(comparative example 7)
Except making liquid hourly space velocity (LHSV) be except 0.02/h, all the other carry out similarly to Example 2.
(comparative example 8)
Except making liquid hourly space velocity (LHSV) be except 4.0/h, all the other carry out similarly to Example 2.
[table 7]
| Comparative example 7 | Embodiment 19 | Embodiment 2 | Embodiment 20 | Comparative example 8 | |
| Liquid hourly space velocity (LHSV) (/h) | 0.02 | 0.05 | 0.3 | 2 | 4 |
| C1-C4 gas (%) | 18.4 | 6.9 | 7.1 | 6.8 | 5.6 |
| Level of residue (%) | 13.1 | 13.8 | 12.3 | 12.7 | 20.9 |
| Decompose oily yield (%) | 50.6 | 60.8 | 63.7 | 62.0 | 55.7 |
Table 7, for illustrating the table of liquid hourly space velocity (LHSV) on the impact of the oily yield of decomposition, illustrated therein is the yield of the amount Sum decomposition oil of the product in comparative example 7, embodiment 19, embodiment 20 and comparative example 8.
Demonstrate thus, liquid hourly space velocity (LHSV) range preferably from 0.05/h ~ 2.0/h.When liquid hourly space velocity (LHSV) is 0.02/h (comparative example 7), processing speed is slow, and treatment effeciency is low, and because 2 times are decomposed, generation oil component being aerified, thus yield is reduced, is therefore not preferred.When liquid hourly space velocity (LHSV) is 4.0/h (comparative example 8), the yield decomposing oil is low, and level of residue is many, therefore can think, shortens the time of contact of catalyst and grease etc. and result in the reduction of grease resolution ratio.
Embodiment 21
Except using the reaction unit of embodiment 3, all the other carry out in the same manner as comparative example 4.In the 1st reaction vessel 32 of reaction unit C, working load has magnesian silica as grease decarboxylation catalyst A33.In 2nd reaction vessel 34, use by the poisoning FCC dead catalyst of Na as grease decarboxylation catalyst B 35.
Be explained, making load similarly to Example 2 has magnesian silica.
Make similarly to Example 11 by the poisoning FCC dead catalyst of Na.
[table 8]
| Embodiment 21 | Comparative example 4 | |
| Oxidizability (mgKOH/g) | 0.33 | 0.55 |
| Iodine number (gl/g) | 23 | 50 |
| Oxidation permanence (h) | ＞24 | 10.1 |
The result of embodiment 21 shown in table 8 and comparative example 4.Be explained, the mensuration of the oxidizability in table 8, iodine number, oxidation permanence is carried out according to the BDF specification bill in the energy resource Room.
By arranging the second reacting furnace, the acid in product is reduced.
[utilizability in industry]
The present invention can provide a kind of like this preparation method of biodiesel fuel, the method, from grease or oil expression raw material, does not need alcohol (auxiliary material), can not by-product glycerol, and the impurity such as dienes and hydroxyl in raw oil material not easily remains in product, the growing amount of coke is few, and the pour point generating oil is also low, also the not easily impurity such as by-product carboxylic acid (free fatty), therefore, be stable to air etc., black change and foreign odor not easily occur, and stability in storage is excellent.In addition, owing to not needing the pretreatment etc. removing free fatty from raw oil material, and can react at ambient pressure, therefore, can seek the simplification of preparation section and the simplification of reaction unit, can provide can in the place construction of necessity for supplying the preparation facilities of the biodiesel fuel of the dispersed-type power sources feed system of the necessary energy.And then, a kind of decarboxylation decomposition catalyst used in biodiesel fuel preparation method can be provided, this catalyst can make, the problem that the activity of the catalyst caused by the free fatty of by-product reduces not easily occurs, can not owing to processing used catalyst or the Appendage Task such as reactivation and cause operating cost to rise or productivity ratio reduces, production efficiency and productivity are all excellent.
[symbol description]
The reaction unit of 1 embodiment 1
2 reaction vessels
3 grease decarboxylation decomposition catalysts
4 heaters
5 raw material throw-in parts
6 flowing gas introduction parts
7 agitating devices
8 the 1st delivery lines
9 decompose oily storage unit
10 discharge pipes
11 cooling tubes
12 cold-trap devices
13 gas outlet pipes
The reaction unit of 21 embodiments 2
22 raw oil material heating parts
23 auxiliary heating portions
The reaction unit of 31 embodiments 3
32 the 1st reaction vessels
33 grease decarboxylation decomposition catalyst A
34 the 2nd reaction vessels
35 grease decarboxylation decomposition catalyst B
38 the 2nd delivery lines
Claims (3)
1. the preparation method of biodiesel fuel, it is characterized in that, the method is at 350 DEG C ~ 475 DEG C, and grease decarboxylation decomposition catalyst and grease or the contact raw that extracts oil in reaction vessel, mainly generate C by above-mentioned grease decarboxylation decomposition catalyst with the decarboxylation decomposition reaction shown in formula 1
8~ C
24hydrocarbon,
Wherein, R
1, R
2, R
3be the alkyl forming grease, represent alkane, alkene;
C
xh
ythe mainly propane of carbon number 3, generates a small amount of methane, ethane, butane in addition;
Described grease decarboxylation decomposition catalyst contains: wantonly more than the a kind product be coated with in wantonly more than the a kind hydroxide by magnesium in the mixture that the carbon activated, activated charcoal, aluminium oxide, silica, non-acid sexual type zeolite, clay mineral and the complex by them by alkali modification are formed, oxide, carbonate
Described oil expression raw material be intracellular deposits grease algae or oil expression before or extract oil after fruit or seed.
2. the preparation method of biodiesel fuel according to claim 1, is characterized in that, above-mentioned grease or above-mentioned oil expression raw material were heated to 350 DEG C ~ 475 DEG C there is decarboxylation decomposition reaction in contact before.
3. the preparation method of the biodiesel fuel described in claim 1 or 2, is characterized in that, in above-mentioned decarboxylation decomposition reaction, coexist H
2o/ grease is with the water vapour of molar ratio computing 1/10 ~ 10/1.
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| PCT/JP2009/005669 WO2010050186A1 (en) | 2008-10-31 | 2009-10-27 | Method and apparatus for manufacturing biodiesel fuel, and decomposition catalyst for decarboxylation of fats used in the method |
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| JP5623928B2 (en) * | 2011-02-07 | 2014-11-12 | 株式会社タクマ | Diesel fuel production system and diesel fuel production method |
| JP5628713B2 (en) * | 2011-03-11 | 2014-11-19 | 株式会社タクマ | Diesel fuel production refiner and purification method, diesel fuel production system and production method using the same |
| JP6004378B2 (en) * | 2011-11-08 | 2016-10-05 | 公益財団法人北九州産業学術推進機構 | Catalytic cracking catalyst |
| CN103614155B (en) * | 2013-09-11 | 2016-08-10 | 浙江工业大学 | A kind of algae oil produces the preparation method of HC fuel |
| CN103509587B (en) * | 2013-09-26 | 2014-12-10 | 太原理工大学 | Method for preparing coal flotation agent by using animal and plant grease and waste oil |
| CN103484143B (en) * | 2013-09-29 | 2015-07-22 | 广西大学 | Method for preparing biodiesel by using FCC spent catalyst loaded acid to catalyze cracking of black rosin |
| JP6332860B2 (en) * | 2014-10-08 | 2018-05-30 | 公益財団法人北九州産業学術推進機構 | Method for refining hydrocarbon oil |
| CN112189046B (en) * | 2018-05-18 | 2023-03-28 | 一般社团法人HiBD研究所 | Method for producing bio-jet fuel |
| CN110041978A (en) * | 2019-04-30 | 2019-07-23 | 蔡国宇 | A kind of preparation method of vapor-permeable type high burning efficiency biological particles |
| JP2021066860A (en) * | 2019-10-23 | 2021-04-30 | 株式会社Ｒｔａ | Method for thermal decomposition liquefaction of waste plastics |
| WO2021193887A1 (en) * | 2020-03-25 | 2021-09-30 | バイオ燃料技研工業株式会社 | Method for producing biodiesel fuel |
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