CN106433999B - A kind of preparation method of renewable hydrocarbon-rich liquid fuel - Google Patents
A kind of preparation method of renewable hydrocarbon-rich liquid fuel Download PDFInfo
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- CN106433999B CN106433999B CN201610402123.7A CN201610402123A CN106433999B CN 106433999 B CN106433999 B CN 106433999B CN 201610402123 A CN201610402123 A CN 201610402123A CN 106433999 B CN106433999 B CN 106433999B
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- 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
- C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
- C11C3/10—Ester interchange
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
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Abstract
The present invention relates to a kind of preparation methods of renewable hydrocarbon-rich liquid fuel, belong to biomass energy transformation technology field.Purpose is to provide for a kind of simple process, reaction condition the hydrocarbon-rich fuel oil preparation method high compared with mild, product light hydrocarbons content.In the presence of a inert carrier gas, waste grease raw material after preheating is added in the reactor equipped with 1~15g composite multi-functional solid acid catalyst, 200~600 DEG C of reaction temperature, carries out catalytic pyrolysis under condition of normal pressure.It is collected after condensation and obtains product liquid i.e. hydrocarbon-rich liquid fuel.Compared with the prior art, the method of the present invention carries out one-step catalytic conversion using composite multi-functional solid acid catalyst, the catalyst has esterification, the multi-functionals such as decarboxylation, activated c-c key and aromatisation, and products therefrom classification and distribution can pass through process conditions appropriate regulation.And the hydrocarbon-rich fuel oil of preparation has higher light hydrocarbon yield.
Description
Technical field
The invention belongs to biomass energy transformation technology fields, relate generally to a kind of preparation of renewable hydrocarbon-rich liquid fuel
Method.
Background technique
With the development of modern chemical industry, hydrocarbon fuel mostlys come from the fractionation and its catalysis of petrochemical industry Crude Oil
Conversion.In recent years, research focus is focused primarily upon using biomass as raw material, Fuel Alcohol Development, biodiesel, biological Hydrogen Energy etc.
Biomass energy and Biomass-based chemicals mention to safeguard national security with economic development to alleviate following energy crisis
For strong technical support.Biomass be can uniquely substitute fossil resource directly convert obtain liquid fuel and chemicals can
Regenerated resources, currently, to receive people more and more extensive for the research of biomass material direct catalytic conversion preparation hydrocarbon fuel
Concern.
In recent years, highly developed using the transesterification preparation biodiesel technology of triglycerides, and formed
Standby technical system.Biodiesel is considered a kind of with the novel biomass energy that potential is widely applied, but due to its knot
The restriction of structure qualitative defect, cost of material, development enter a bottleneck.The bottleneck that breaking can mould one it is new
Platform.Using waste grease as raw material, direct catalytic pyrolysis conversion prepares hydrocarbon product, on the basis for being sufficiently reserved its linear chain structure
Under, carbonyl is sloughed, carries out aromatisation while suitably shortening carbon chain lengths, which is not only biomass grease exploitation benefit
With providing new thinking, and breach the traditional source of hydrocarbon fuel, moreover it is possible to adjust existing energy resource structure, meet environment friend
The requirement of zero carbon emission promotes biomass comprehensive using development, final to realize the sustainable development of China's economy and society.
At present with grease type catalytic material convert preparation HC fuel research focus primarily upon direct high temperature pyrolysis chain rupture,
Noble metal catalyst catalytic hydrodeoxygenation, fat saponification are at catalytic decarboxylation after salt etc..There is productions for direct high temperature pyrolytic cracking (HTP)
The problems such as object is selectively poor, saturated hydrocarbons are few, oxygen-bearing organic matter is more in product；Patent 102417824A discloses a kind of hydro carbons
The preparation method of fuel mainly provides one kind in a hydrogen atmosphere, with TiO2For the direct catalyzed oil of ruthenium-based catalyst of carrier
The method of rouge hydrogenation deoxidation, the method liquid yield is higher, but catalyst higher cost, and security risk is higher；Patent
103361102A discloses a kind of method for preparing liquid hydrocarbon product, and the soap salt for mainly providing grease formation is made in molten caustic soda
With the lower technique that decarboxylic reaction occurs, patent 102268280A discloses a kind of micro ware auxiliary catalysis soaps decarboxylation method and prepares hydro carbons
The technique of hydrocarbon fuel is produced in the method for fuel, exploitation microwave selective pyrolysis, and energy consumption is higher in the prior art for solution, catalyst
The problems such as being easy inactivation.But by our comparison, this method preparation needs two steps, and process flow is more complex.
Summary of the invention
In order to overcome the shortcomings of background technique, the present invention provides a kind of preparation methods of renewable hydrocarbon-rich liquid fuel.
Mainly solves the problems such as existing method preparation hydrocarbon fuel complex process, selectivity of product is low, catalyst is at high cost.
The technical scheme adopted by the invention is that: a kind of preparation method of renewable hydrocarbon-rich liquid fuel, including following step
It is rapid:
(1) in the presence of a inert carrier gas, by waste grease raw material after preheating and certain proportion methyl alcohol mixed liquor to set stream
Speed is pumped into the composite multi-functional solid acid catalyst reactor for being pre-loaded with 1~15g, and 200~600 DEG C of reaction temperature, often
Catalytic pyrolysis is carried out under the conditions of pressure；
(2) cracking steam generated in step (1) is collected after gradient freezing and obtains the i.e. renewable hydrocarbon-rich of product
Liquid fuel.
In process provided by the invention, waste grease raw material described in step (1) includes inedible woody
Grease, expired food oil, acidification oil, gutter oil, waste oil from restaurants, microalgae grease etc..
In process provided by the invention, reactor described in step (1) includes fixed-bed reactor, closed
Reaction kettle device, fluidized bed reaction.
In process provided by the invention, inert carrier gas described in step (1) is N2, CO2, a kind of or several in He, Ar
Kind.
In process provided by the invention, catalyst described in step (1) is composite multi-functional solid acid.
In process provided by the invention, composite solid acid described in step (1) be IIA, IIIA, IVA,
SO is loaded on the composite oxides of two or more metallic elements in IIB, IVB, VIB, VIIB, VIII4 2-。
In process provided by the invention, gradient freezing described in step (2) is by 10 DEG C of condenser pipes, 0 DEG C of ice
Bath, -220 DEG C of liquid nitrogen three-level gradient freezings.
In process provided by the invention, product made from catalytic pyrolysis described in step (2) is mainly carbon atom
The mixture of the hydro carbons such as alkane, alkene, the aromatic hydrocarbons of number 6~24.
The invention difference from existing technology is that the present invention achieves following technical effect: constant flow rate 10~
Under the conditions of 300 μ L/min and inert carrier gas are existing, after glyceride stock after preheating and the preheating of certain proportion methyl alcohol mixed liquor
It is pumped into the composite multi-functional solid acid catalyst reactor for being pre-loaded with 1~15g, 200~600 DEG C of reaction temperature, normal pressure
Under the conditions of carry out catalytic pyrolysis, it is last caused by cracking steam successively pass through 10 DEG C of condenser pipes, 0 DEG C of ice bath slot, -220 DEG C of liquid
The i.e. renewable hydrocarbon-rich liquid fuel of product liquid is obtained after nitrogen gradient freezing.Hydrocarbon-rich fuel oil preparation method provided by the invention uses
Composite multi-functional solid acid catalyst carries out one-step catalytic conversion, and simple process, reaction condition be relatively mild, catalyst preparation
Simply, and the catalyst has esterification, and the multi-functionals such as decarboxylation, activated c-c key and aromatisation are easy reclaiming and again
Still there is good catalytic activity, prepared hydrocarbon-rich fuel oil has higher light hydrocarbon yield after 15 times multiple.Below with fixed bed
For reactor, in conjunction with attached drawing, the invention will be further described.
Detailed description of the invention
Fig. 1 is Experimental equipment of the present invention.1- raw material storage tank, 2- thermostat water bath, the micro constant flow pump of 3-, 4- triple valve,
5- gas flowmeter, 6- gas cylinder a, 7- gas cylinder b, 8- heating device, 9- fixed bed reaction pipe, 10- digital display type temperature controller, 11- are cold
Solidifying pipe, 12- liquid header, 13- ice bath slot, 14-U type pipe, 15- Dewar bottle, 16- exhaust gas processing device.
Fig. 2 is the gas chromatogram in the Gc-mss of the civilian 0# diesel oil in China.
Fig. 3 is the gas chromatogram in waste grease in the Gc-mss of 300 DEG C of acidification oil esterification pyrolysis products.
Fig. 4 is the gas chromatogram in waste grease in the Gc-mss of 350 DEG C of catalytic pyrolysis products of acidification oil.
Fig. 5 is the gas chromatogram in waste grease in the Gc-mss of 450 DEG C of catalytic pyrolysis products of acidification oil.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, technical matters step, condition and material is embodied, to this hair
Technical solution in bright embodiment is clearly and completely described, it is clear that described embodiment is only present invention a part
Embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not paying wound
Every other embodiment obtained under the premise of the property made labour, shall fall within the protection scope of the present invention.
The present invention uses glyceride stock for inedible woody grease, expired food oil, acidification oil, gutter oil, food and drink
Abandoned oil, microalgae grease etc..Inert carrier gas 6 or 7 is passed into reaction tube 9 by triple valve 4, while will be in raw material storage tank 1
Glyceride stock and certain proportion methyl alcohol mixed liquor through thermostat water bath 2 preheating after, by constant flow pump 3 with constant flow rate be 10~
300 μ L/min are pumped into fixed bed reaction pipe 9, are covered with 0.1~2cm above the quartz sand layer in the middle part of Φ 3cm quartz ampoule in advance
The composite multi-functional solid acid catalyst bed of height, controlling temperature at bed by digital display type thermometer 10 is 200~600
DEG C, last generated cracking steam successively passes through 10 DEG C of condenser pipes, 11,0 DEG C of ice bath slot 12, -220 DEG C of 14 gradient freezings of liquid nitrogen
After obtain product liquid i.e. hydrocarbon-rich liquid fuel.
Embodiment 1
By certain mass SnCl2·2H2O and ZrOCl2·8H2O is dissolved in 1000 milliliters of deionized water, it is to be dissolved after
Concentrated ammonia liquor is slowly added dropwise under stirring as precipitating reagent, adjusting solution ph to 8~9 obtains tin-zirconium hydroxide precipitating,
Room temperature is aged for 24 hours.After the completion of ageing, precipitating is washed with deionized, filters, up to no Cl-In the presence of.By sediment at 105 DEG C
Drying for 24 hours, then is ground to 100 mesh or less.It is impregnated for 24 hours, is then filtered to remove excessive with the 1mol/L sulfuric acid solution newly prepared
Sulfuric acid solution, and dried for 24 hours at 105 DEG C.Obtained solid is placed in quartz ampoule after 700 DEG C of roasting 3h, to be obtained under the conditions of logical oxygen
To composite multi-functional solid acid catalyst SO4 2-/SnO2-ZrO2, bottle, be placed in spare in drier after cooling.
Embodiment 2
By certain mass TiCl4And ZrOCl2·8H2O is dissolved in 1000 milliliters of deionized water, is stirring shape after to be dissolved
Concentrated ammonia liquor is slowly added dropwise under state as precipitating reagent, adjusts solution ph to 8~9, obtains tin-zirconium hydroxide precipitating, room temperature is old
Change for 24 hours.After the completion of ageing, precipitating is washed with deionized, filters, up to no Cl-In the presence of.By sediment in 105 DEG C of dryings
For 24 hours, 100 mesh or less are ground to then.It is impregnated for 24 hours with the 1mol/L sulfuric acid solution newly prepared, is then filtered to remove excessive sulfuric acid
Solution, and dried for 24 hours at 105 DEG C.Obtained solid is placed in quartz ampoule after 700 DEG C of roasting 3h, is answered under the conditions of logical oxygen
Mould assembly multifunctional solid acid catalyst SO4 2-/TiO2-ZrO2, bottle, be placed in spare in drier after cooling.
Embodiment 3
By certain mass Ce (NO3)3·6H2O and ZrOCl2·8H2O is dissolved in 1000 milliliters of deionized water, after to be dissolved
Concentrated ammonia liquor is slowly added dropwise under stirring as precipitating reagent, adjusts solution ph to 8~9, it is heavy to obtain tin-zirconium hydroxide
It forms sediment, room temperature is aged for 24 hours.After the completion of ageing, precipitating is washed with deionized, filters, up to no Cl-In the presence of.By sediment 105
It is DEG C dry for 24 hours, then be ground to 100 mesh or less.It is impregnated for 24 hours with the 1mol/L sulfuric acid solution newly prepared, is then filtered to remove excess
Sulfuric acid solution, and at 105 DEG C it is dry for 24 hours.Obtained solid is placed in quartz ampoule under the conditions of logical oxygen after 700 DEG C of roasting 3h,
Obtain composite multi-functional solid acid catalyst SO4 2-/Ce2O3-ZrO2, bottle, be placed in spare in drier after cooling.
Embodiment 4
By certain mass Co (NO3)2·6H2O and ZrOCl2·8H2O is dissolved in 1000 milliliters of deionized water, after to be dissolved
Concentrated ammonia liquor is slowly added dropwise under stirring as precipitating reagent, adjusts solution ph to 8~9, it is heavy to obtain tin-zirconium hydroxide
It forms sediment, room temperature is aged for 24 hours.After the completion of ageing, precipitating is washed with deionized, filters, up to no Cl-In the presence of.By sediment 105
It is DEG C dry for 24 hours, then be ground to 100 mesh or less.It is impregnated for 24 hours with the 1mol/L sulfuric acid solution newly prepared, is then filtered to remove excess
Sulfuric acid solution, and at 105 DEG C it is dry for 24 hours.Obtained solid is placed in quartz ampoule under the conditions of logical oxygen after 700 DEG C of roasting 3h,
Obtain composite multi-functional solid acid catalyst SO4 2-/CoO-ZrO2, bottle, be placed in spare in drier after cooling.
Embodiment 5
By inert carrier gas N2It is passed into fixed bed reaction pipe with constant flow rate 30ml/min, while being 1 by 4.0g molar ratio:
5 acidification oils and methyl alcohol mixed liquor are pumped into for 3ml/h added with 5.0g composite multi-functional solid acid catalyst SO with constant flow rate4 2-/
SnO2-ZrO2Fixed bed reaction pipe in, carry out catalytic pyrolysis under 350 DEG C of temperature, carrier gas nitrogen 40mL/min, condition of normal pressure,
Cracking oil vapour caused by last successively passes through 10 DEG C of condenser pipes, 0 DEG C of ice bath slot, is made and produces after -220 DEG C of liquid nitrogen gradient freezings
Object is mainly fatty acid methyl ester, and oil-phase product yield is 38.48% in gained product liquid, water-phase product yield 6.49%.Oil
Phase product acid value is reduced to 38.64mgKOH/g by the 148.89mgKOH/g of original acidification oil.
Embodiment 6
By inert carrier gas N2It is passed into fixed bed reaction pipe with constant flow rate 30ml/min, while being 1 by 4.0g molar ratio:
5 acidification oils and methyl alcohol mixed liquor are pumped into for 3ml/h added with 5.0g composite multi-functional solid acid catalyst SO with constant flow rate4 2-/
TiO2-ZrO2Fixed bed reaction pipe in, carry out catalytic pyrolysis under 350 DEG C of temperature, carrier gas nitrogen 40mL/min, condition of normal pressure,
Cracking oil vapour caused by last successively passes through 10 DEG C of condenser pipes, 0 DEG C of ice bath slot, is made and produces after -220 DEG C of liquid nitrogen gradient freezings
Object is mainly hydrocarbon-rich fuel oil, and oil-phase product yield is 52.02% in gained product liquid, water-phase product yield 6.66%.Oily phase
Product acid value is reduced to 3.84mgKOH/g by the 148.89mgKOH/g of original acidification oil.
Embodiment 7
By inert carrier gas N2It is passed into fixed bed reaction pipe with constant flow rate 30ml/min, while being 1 by 4.0g molar ratio:
5 acidification oils and methyl alcohol mixed liquor are pumped into for 3ml/h added with 5.0g composite multi-functional solid acid catalyst SO with constant flow rate4 2-/
Ce2O3-ZrO2Fixed bed reaction pipe in, carried out under 350 DEG C of temperature, carrier gas nitrogen 40mL/min, condition of normal pressure catalysis split
Solution, it is last caused by cracking oil vapour successively pass through 10 DEG C of condenser pipes, 0 DEG C of ice bath slot is made after -220 DEG C of liquid nitrogen gradient freezings
Obtaining product is mainly fatty acid methyl ester, and oil-phase product yield is 73.54% in gained product liquid, water-phase product yield
4.04%.Oil-phase product acid value is reduced to 86.99mgKOH/g by the 148.89mgKOH/g of original acidification oil.
Embodiment 8
By inert carrier gas N2It is passed into fixed bed reaction pipe with constant flow rate 30ml/min, while being 1 by 4.0g molar ratio:
5 acidification oils and methyl alcohol mixed liquor are pumped into for 3ml/h added with 5.0g composite multi-functional solid acid catalyst SO with constant flow rate4 2-/
CoO-ZrO2Fixed bed reaction pipe in, carry out catalytic pyrolysis under 350 DEG C of temperature, carrier gas nitrogen 40mL/min, condition of normal pressure,
Cracking oil vapour caused by last successively passes through 10 DEG C of condenser pipes, 0 DEG C of ice bath slot, is made and produces after -220 DEG C of liquid nitrogen gradient freezings
Object is mainly fatty acid methyl ester, and oil-phase product yield is 73.54% in gained product liquid, water-phase product yield 4.04%.Oil
Phase product acid value is reduced to 80.02mgKOH/g by the 148.89mgKOH/g of original acidification oil.
Embodiment 9
By inert carrier gas N2It is passed into fixed bed reaction pipe with constant flow rate 30ml/min, while being 1 by 4.0g molar ratio:
5 acidification oils and methyl alcohol mixed liquor are pumped into for 3ml/h added with 5.0g composite multi-functional solid acid catalyst SO with constant flow rate4 2-/
TiO2-ZrO2Fixed bed reaction pipe in, carry out catalytic pyrolysis under 300 DEG C of temperature, carrier gas nitrogen 40mL/min, condition of normal pressure,
Cracking oil vapour caused by last successively passes through 10 DEG C of condenser pipes, 0 DEG C of ice bath slot, is made and produces after -220 DEG C of liquid nitrogen gradient freezings
Object is mainly fatty acid methyl ester, and oil-phase product yield is 56.25% in gained product liquid, water-phase product yield 4.23%.Oil
Phase product acid value is reduced to 21.78mgKOH/g by the 148.89mgKOH/g of original acidification oil.
Embodiment 10
By inert carrier gas N2It is passed into fixed bed reaction pipe with constant flow rate 30ml/min, while being 1 by 4.0g molar ratio:
5 acidification oils and methyl alcohol mixed liquor are pumped into for 3ml/h added with 5.0g composite multi-functional solid acid catalyst SO with constant flow rate4 2-/
TiO2-ZrO2Fixed bed reaction pipe in, carry out catalytic pyrolysis under 400 DEG C of temperature, carrier gas nitrogen 40mL/min, condition of normal pressure,
Cracking oil vapour caused by last successively passes through 10 DEG C of condenser pipes, 0 DEG C of ice bath slot, is made and produces after -220 DEG C of liquid nitrogen gradient freezings
Object is mainly based on hydrocarbon-rich fuel oil and hydrocarbon product, and oil-phase product yield is 65.85% in gained product liquid, and water-phase product obtains
Rate 7.73%.Oil-phase product acid value is reduced to 7.05mgKOH/g by the 148.89mgKOH/g of original acidification oil.
Embodiment 11
By inert carrier gas N2It is passed into fixed bed reaction pipe with constant flow rate 30ml/min, while being 1 by 4.0g molar ratio:
5 acidification oils and methyl alcohol mixed liquor are pumped into for 3ml/h added with 5.0g composite multi-functional solid acid catalyst SO with constant flow rate4 2-/
TiO2-ZrO2Fixed bed reaction pipe in, carry out catalytic pyrolysis under 450 DEG C of temperature, carrier gas nitrogen 40mL/min, condition of normal pressure,
Cracking oil vapour caused by last successively passes through 10 DEG C of condenser pipes, 0 DEG C of ice bath slot, is made and produces after -220 DEG C of liquid nitrogen gradient freezings
Object is mainly hydrocarbon-rich fuel oil and product based on aromatic hydrocarbons, and oil-phase product yield is 44.36% in gained product liquid, water-phase product
Yield 2.02%.Oil-phase product acid value is reduced to 6.03mgKOH/g by the 148.89mgKOH/g of original acidification oil.
Embodiment 12
By inert carrier gas N2It is passed into fixed bed reaction pipe with constant flow rate 30ml/min, while being 1 by 4.0g molar ratio:
5 acidification oils and methyl alcohol mixed liquor are pumped into for 3ml/h added with 5.0g composite multi-functional solid acid catalyst SO with constant flow rate4 2-/
TiO2-ZrO2Fixed bed reaction pipe in, carry out catalytic pyrolysis under 500 DEG C of temperature, carrier gas nitrogen 40mL/min, condition of normal pressure,
Cracking oil vapour caused by last successively passes through 10 DEG C of condenser pipes, 0 DEG C of ice bath slot, is made and produces after -220 DEG C of liquid nitrogen gradient freezings
Object is mainly hydrocarbon-rich fuel oil and product based on aromatic hydrocarbons, and oil-phase product yield is 30.87% in gained product liquid, water-phase product
Yield 7.41%.Oil-phase product acid value is reduced to 6.03mgKOH/g by the 148.89mgKOH/g of original acidification oil.
Embodiment 13
By inert carrier gas N2It is passed into fixed bed reaction pipe with constant flow rate 30ml/min, while 4.0g suitably being pre-processed
Jatropha curcas fruit expressed oil afterwards is directly that 3ml/h is pumped into added with 5.0g composite multi-functional solid acid catalysis with constant flow rate
Agent SO4 2-/TiO2-ZrO2Fixed bed reaction pipe in, urged under 400 DEG C of temperature, carrier gas nitrogen 40mL/min, condition of normal pressure
Change cracking, last generated cracking oil vapour successively passes through 10 DEG C of condenser pipes, 0 DEG C of ice bath slot, -220 DEG C of liquid nitrogen gradient freezings
It is mainly hydrocarbon-rich fuel oil that product is made afterwards, and oil-phase product yield is 70.72% in gained product liquid, almost without water-phase product.
Biomass carbon yield is 6.35%, gas yield 22.93%
Embodiment 14
By inert carrier gas N2It is passed into fixed bed reaction pipe with constant flow rate 30ml/min, while 4.0g suitably being pre-processed
Rubber seed expressed oil afterwards is directly that 3ml/h is pumped into added with 5.0g composite multi-functional solid acid catalyst with constant flow rate
SO4 2-/TiO2-ZrO2Fixed bed reaction pipe in, be catalyzed under 400 DEG C of temperature, carrier gas nitrogen 40mL/min, condition of normal pressure
Cracking, it is last caused by cracking oil vapour successively pass through i0 DEG C of condenser pipe, 0 DEG C of ice bath slot, after -220 DEG C of liquid nitrogen gradient freezings
Obtained product is mainly hydrocarbon-rich fuel oil, and oil-phase product yield is 69.85% in gained product liquid, almost without water-phase product.It is raw
Substance charcoal yield is 8.15%, gas yield 22.00%.Oil-phase product acid value by original rubber seed oil 22.96mgKOH/
G is reduced to 5.46mgKOH/g.
Embodiment 15
By inert carrier gas N2It is passed into fixed bed reaction pipe with constant flow rate 30ml/min, while 4.0g suitably being pre-processed
Tung oil afterwards is directly that 3ml/h is pumped into added with 5.0g composite multi-functional solid acid catalyst SO with constant flow rate4 2-/TiO2-
ZrO2Fixed bed reaction pipe in, carry out catalytic pyrolysis under 400 DEG C of temperature, carrier gas nitrogen 40mL/min, condition of normal pressure, finally
Generated cracking oil vapour successively passes through 10 DEG C of condenser pipes, 0 DEG C of ice bath slot, and product master is made after -220 DEG C of liquid nitrogen gradient freezings
Will be for hydrocarbon-rich fuel oil and product is based on aromatic hydrocarbons, oil-phase product yield is 69.13% in gained product liquid, is produced almost without water phase
Object.Biomass carbon yield is 7.68%, gas yield 23.19%.
Embodiment 16
By inert carrier gas N2It is passed into fixed bed reaction pipe with constant flow rate 30ml/min, while 4.0g suitably being pre-processed
Gutter oil afterwards is directly that 3ml/h is pumped into added with 5.0g composite multi-functional solid acid catalyst SO with constant flow rate4 2-/
TiO2-ZrO2Fixed bed reaction pipe in, carry out catalytic pyrolysis under 400 DEG C of temperature, carrier gas nitrogen 40mL/min, condition of normal pressure,
Cracking oil vapour caused by last successively passes through 10 DEG C of condenser pipes, 0 DEG C of ice bath slot, is made and produces after -220 DEG C of liquid nitrogen gradient freezings
Object is mainly hydrocarbon-rich fuel oil, and oil-phase product yield is 64.65% in gained product liquid, almost without water-phase product.Biomass carbon
Yield is 7.44%, gas yield 27.91%.Oil-phase product acid value is reduced by the 99.11mgKOH/g of original rubber seed oil
For 4.54mgKOH/g.
Every technical staff's notice: of the invention although the present invention is described according to above-mentioned specific embodiment
Invention thought be not limited in the invention, any repacking with inventive concept will all be included in this patent protection of the patent right
In range.
Claims (5)
1. a kind of preparation method of renewable hydrocarbon-rich liquid fuel, comprising the following steps:
(1) in the presence of a inert carrier gas, by waste grease raw material after preheating and certain proportion methyl alcohol mixed liquor to set flow pump
Enter to be pre-loaded in the composite multi-functional solid acid catalyst reactor of 1~15g, 400~600 DEG C of reaction temperature, normal pressure item
Catalytic pyrolysis is carried out under part；
Multifunctional solid acid catalyst described in step (1) is SO4 2-/TiO2-ZrO2；
(2) cracking steam generated in step (1) is collected after gradient freezing and obtains the i.e. renewable hydrocarbon-rich liquid of product
Fuel.
2. a kind of preparation method of renewable hydrocarbon-rich liquid fuel according to claim 1, it is characterised in that described in step (1)
Waste grease raw material is inedible woody grease, expired food oil, acidification oil, gutter oil, waste oil from restaurants or microalgae oil
Rouge.
3. a kind of preparation method of renewable hydrocarbon-rich liquid fuel according to claim 1, it is characterised in that described in step (1)
Reactor is fixed-bed reactor, confined reaction kettle device or fluidized bed reaction.
4. a kind of preparation method of renewable hydrocarbon-rich liquid fuel according to claim 1, it is characterised in that described in step (1)
Inert carrier gas is N2, CO2, one or more of in He, Ar.
5. a kind of preparation method of renewable hydrocarbon-rich liquid fuel according to claim 1, it is characterised in that described in step (2)
Gradient freezing is by 10 DEG C of condenser pipes, 0 DEG C of ice bath slot, -220 DEG C of liquid nitrogen three-level gradient freezings.
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| CN108640822B (en) * | 2018-04-25 | 2021-10-22 | 铜仁学院 | Preparation method of 4-vinyl guaiacol and 4-vinyl guaiacol |
| CN110257098A (en) * | 2019-06-25 | 2019-09-20 | 中国林业科学研究院林产化学工业研究所 | A kind of method that bio-oil thermochemical study reduces reaction activity preparation biological Aviation Fuel and biodiesel |
| CN116836757A (en) * | 2023-08-14 | 2023-10-03 | 平湖市晨星科技实业有限公司 | Method for producing biodiesel by utilizing rare earth compound and solid super acidic catalyst |
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| CN1710026A (en) * | 2005-06-24 | 2005-12-21 | 清华大学 | Technical method for preparing biodiesel using reactive separation process coupling technique |
| CN102206502A (en) * | 2010-03-31 | 2011-10-05 | 中国石油化工股份有限公司 | Preparation method of aromatic hydrocarbons and low-carbon olefins through co-processing animal and plant oils and oxygenated chemical |
| CN103710155A (en) * | 2013-12-13 | 2014-04-09 | 中国林业科学研究院林产化学工业研究所 | Method for preparing biodiesel through high-temperature esterification reaction of high acid value oil |
| CN105175205A (en) * | 2015-07-14 | 2015-12-23 | 南京林业大学 | Method for preparing aromatic hydrocarbon through catalytic aromatization of carboxylic acid methyl ester prepared from biomass oil |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1710026A (en) * | 2005-06-24 | 2005-12-21 | 清华大学 | Technical method for preparing biodiesel using reactive separation process coupling technique |
| CN102206502A (en) * | 2010-03-31 | 2011-10-05 | 中国石油化工股份有限公司 | Preparation method of aromatic hydrocarbons and low-carbon olefins through co-processing animal and plant oils and oxygenated chemical |
| CN103710155A (en) * | 2013-12-13 | 2014-04-09 | 中国林业科学研究院林产化学工业研究所 | Method for preparing biodiesel through high-temperature esterification reaction of high acid value oil |
| CN105175205A (en) * | 2015-07-14 | 2015-12-23 | 南京林业大学 | Method for preparing aromatic hydrocarbon through catalytic aromatization of carboxylic acid methyl ester prepared from biomass oil |
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