CN106433999A - Preparation method of renewable hydrocarbon-rich liquid fuel - Google Patents
Preparation method of renewable hydrocarbon-rich liquid fuel Download PDFInfo
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- CN106433999A CN106433999A CN201610402123.7A CN201610402123A CN106433999A CN 106433999 A CN106433999 A CN 106433999A CN 201610402123 A CN201610402123 A CN 201610402123A CN 106433999 A CN106433999 A CN 106433999A
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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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- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method of a renewable hydrocarbon-rich liquid fuel, and belongs to the technical field of biomass energy conversion. The purpose of the invention is to provide the preparation method of the hydrocarbon-rich liquid fuel, with the advantages of simple process, mild reaction conditions, and high content of lightweight hydrocarbons in the above product. The method comprises the following steps: adding a preheated waste oil raw material into a reactor filled with 1-15 g of a compound multifunctional solid acid catalyst in the presence of an inert carrier gas, and carrying out catalytic cracking at a reaction temperature of 200-600 DEG C under normal pressure; and condensing the obtained reaction product, and collecting obtained liquid product to obtain the hydrocarbon-rich liquid fuel. The compound multifunctional solid acid catalyst is adopted by the method to carry out one-step catalytic conversion, and has esterification, decarboxylation, carbon-carbon bond activation and aromatization functions, and the type and the distribution of the obtained product can be properly regulated through regulating technologic conditions. The prepared hydrocarbon-rich fuel has a high lightweight hydrocarbon yield.
Description
Technical field
The invention belongs to biomass energy transformation technology field, relates generally to a kind of preparation of renewable richness hydrocarbon liquid fuel
Method.
Background technology
With the development of modern chemical industry, hydrocarbon fuel mostlys come from the fractional distillation of petrochemical industry Crude Oil and its catalysis
Conversion.In recent years, research focus are focused primarily upon with biomass as raw material, Fuel Alcohol Development, biodiesel, biological Hydrogen Energy etc.
Biomass energy and Biomass-based chemicals, to alleviating following energy crisis, carry with economic development for safeguarding national security
For strong technical support.Biomass be can uniquely substitute fossil resource directly conversion obtain liquid fuel and chemicals can
Regenerated resources, at present, biomass material direct catalytic conversion prepares the research of hydrocarbon fuel, and to receive people more and more extensive
Concern.
In recent years, highly developed using the transesterification biodiesel technology for preparing of triglyceride, and formed
Standby technical system.Biodiesel is considered as a kind of novel biomass energy with extensive application potential, but due to its knot
The qualitative defect of structure, the restriction of cost of material, its development enters a bottleneck.Break this bottleneck can mould one new
Platform.With waste grease as raw material, direct catalytic pyrolysiss conversion prepares hydrocarbon product, on the basis for being sufficiently reserved its linear chain structure
Under, carbonyl to be sloughed, while suitably shortening carbon chain lengths, aromatisation is carried out, the catalyzed conversion is not only biomass oils and fatss exploitation profit
With new thinking is provided, and the traditional source of hydrocarbon fuel being breached, moreover it is possible to adjust existing energy resource structure, meets environment friend
Zero carbon emission is required, is promoted biomass comprehensive using development, is finally realized China's economy and society sustainable development.
Converted with oils catalytic material at present prepare HC fuel research focus primarily upon direct high temperature pyrolysis chain rupture,
Noble metal catalyst catalytic hydrodeoxygenation, fat saponification become the aspect such as catalytic decarboxylation after salt.Directly high temperature pyrolytic cracking (HTP) has product
The problems such as thing selectivity is poor, saturated hydrocarbons are few, oxygen-bearing organic matter is many in product；Patent 102417824A discloses a kind of hydro carbons
The preparation method of fuel, mainly provides one kind in a hydrogen atmosphere, with TiO2The direct catalyzed oil of ruthenium-based catalyst for carrier
The method of fat hydrogenation deoxidation, the method liquid yield is higher, but catalyst is relatively costly, and potential safety hazard is higher；Patent
103361102A discloses a kind of method for preparing liquid hydrocarbon product, and the main soap salt for providing oils and fatss 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 method of fuel, develops the technique that hydrocarbon fuel is produced in microwave selective pyrolysis, and in solution prior art, energy consumption is higher, catalyst
The problems such as easily inactivating.But by our contrast, prepared by the method need two steps, and technological process is more complicated.
Content of the invention
In order to overcome the shortcomings of background technology, the invention provides a kind of preparation method of renewable richness hydrocarbon liquid fuel.
Mainly solve existing method prepare that hydrocarbon fuel complex process, selectivity of product be low, catalyst high cost the problems such as.
The technical solution adopted in the present invention is：A kind of preparation method of renewable richness hydrocarbon liquid fuel, including following step
Suddenly：
(1) in the presence of a inert carrier gas, by waste grease raw material after preheating with certain proportion methyl alcohol mixed liquor to set stream
Speed is pumped into and is pre-loaded with the composite multi-functional solid acid catalyst reactor of 1～15g, 200～600 DEG C of reaction temperature, often
Catalytic pyrolysiss are carried out under the conditions of pressure；
(2) produced cracking steam in step (1) is collected after gradient freezing and obtains product i.e. renewable richness hydrocarbon
Liquid fuel.
In the process that the present invention is provided, the waste grease raw material described in step (1) includes inedible woody
Oils and fatss, expired food oil, acidification oil, waste oil, food and drink abandoned oil, microalgae grease etc..
In the process that the present invention is provided, the reactor described in step (1) includes fixed-bed reactor, closed
Reaction kettle device, fluidized bed reaction.
In the process that the present invention is provided, the inert carrier gas described in step (1) is N2, CO2, a kind of or several in He, Ar
Kind.
In the process that the present invention is provided, the catalyst described in step (1) is composite multi-functional solid acid.
The present invention provide process in, the composite solid acid described in step (1) be IIA, IIIA, IVA,
SO is loaded in IIB, IVB, VIB, VIIB, VIII on the composite oxides of two or more metallic elements4 2-.
The present invention provide process in, the gradient freezing described in step (2) be through 10 DEG C of condensing tubes, 0 DEG C of ice
Bath, -220 DEG C of liquid nitrogen three-level gradient freezings.
In the process that the present invention is provided, product obtained in the catalytic pyrolysiss described in step (2) is mainly carbon atom
The mixture of the hydro carbons such as the alkane of number 6～24, alkene, aromatic hydrocarbons.
The invention difference from existing technology is, the present invention achieves following technique effect：Constant flow rate 10～
Under conditions of 300 μ L/min and inert carrier gas are present, after after preheating, glyceride stock is preheated with certain proportion methyl alcohol mixed liquor
Pump into and be pre-loaded with the composite multi-functional solid acid catalyst reactor of 1～15g, 200～600 DEG C of reaction temperature, normal pressure
Under the conditions of carry out catalytic pyrolysiss, last produced by cracking steam sequentially pass through 10 DEG C of condensing tubes, 0 DEG C of ice bath groove, -220 DEG C of liquid
Product liquid i.e. renewable richness hydrocarbon liquid fuel is obtained after nitrogen gradient freezing.The rich hydrocarbon fuel oil preparation method that the present invention is provided is adopted
Composite multi-functional solid acid catalyst carries out one-step catalytic conversion, process is simple, reaction condition relatively gentle, catalyst preparation
Simply, and the catalyst has esterification, the multi-functional such as decarboxylation, activated c-c key and aromatisation, easy reclaiming and weight
Still there is after multiple 15 times good catalytic activity, prepared rich hydrocarbon fuel oil has higher light hydrocarbon yield.Below with fixed bed
As a example by reactor, in conjunction with accompanying drawing, the invention will be further described.
Description of the drawings
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- three-way valve,
5- gas flowmeter, 6- gas cylinder a, 7- gas cylinder b, 8- heater, 9- fixed bed reaction pipe, 10- digital display type temperature controller, 11- is cold
Solidifying pipe, 12- liquid header, 13- ice bath groove, 14-U type pipe, 15- Dewar flask, 16- exhaust gas processing device.
Fig. 2 is the gas chromatogram in the Gc-mss of the civilian 0# diesel oil of China.
Fig. 3 is the gas chromatogram in waste grease in the Gc-mss of 300 DEG C of esterification pyrolysis products of acidification oil.
Fig. 4 is the gas chromatogram in waste grease in the Gc-mss of 350 DEG C of catalytic pyrolysiss products of acidification oil.
Fig. 5 is the gas chromatogram in waste grease in the Gc-mss of 450 DEG C of catalytic pyrolysiss products of acidification oil.
Specific embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, technical matters step, condition and material is embodied as, to this
Technical scheme in bright embodiment is clearly and completely described, it is clear that described embodiment is only a present invention part
Embodiment, rather than whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art are not paying wound
The every other embodiment for being obtained under the premise of the property made work, belongs to the scope of protection of the invention.
The present invention is inedible woody oils and fatss, expired food oil, acidification oil, waste oil, food and drink using glyceride stock
Abandoned oil, microalgae grease etc..Inert carrier gas 6 or 7 is passed in reaction tube 9 by three-way valve 4, while by raw material storage tank 1
Glyceride stock and certain proportion methyl alcohol mixed liquor after the preheating of thermostat water bath 2, by constant flow pump 3 with constant flow rate as 10～
300 μ L/min are pumped in fixed bed reaction pipe 9, are covered with 0.1～2cm in advance above the quartz sand layer in the middle part of Φ 3cm quartz ampoule
The composite multi-functional solid acid catalyst bed of height, it is 200～600 to control temperature at bed by digital display type thermometer 10
DEG C, last produced cracking steam sequentially passes through 10 DEG C of condensing tubes, 11,0 DEG C of ice bath groove 12, -220 DEG C of 14 gradient freezings of liquid nitrogen
After obtain product liquid i.e. rich hydrocarbon liquid fuel.
Embodiment 1
By certain mass SnCl2·2H2O and ZrOCl2·8H2O is dissolved in 1000 milliliters of deionized water, to be dissolved after
Strong aqua ammonia being slowly added dropwise under stirring as precipitant, adjusts solution ph to 8～9, obtain stannum-zirconium hydroxide precipitation,
Room temperature is aged 24h.After the completion of ageing, precipitation is washed with deionized, sucking filtration, until no Cl-Exist.By precipitate at 105 DEG C
24h is dry, then is ground to below 100 mesh.24h being impregnated with the new 1mol/L sulfuric acid solution for preparing, is then filtered to remove excessive
Sulfuric acid solution, and 24h is dry at 105 DEG C.Gained solid is placed in quartz ampoule under the conditions of logical oxygen after 700 DEG C of roasting 3h, is obtained
To composite multi-functional solid acid catalyst SO4 2-/SnO2-ZrO2, bottle after cooling, be placed in standby in exsiccator.
Embodiment 2
By certain mass TiCl4And ZrOCl2·8H2O is dissolved in 1000 milliliters of deionized water, to be dissolved after stirring shape
Strong aqua ammonia being slowly added dropwise under state as precipitant, adjusting solution ph to 8～9, obtain stannum-zirconium hydroxide precipitation, room temperature is old
Change 24h.After the completion of ageing, precipitation is washed with deionized, sucking filtration, until no Cl-Exist.By precipitate in 105 DEG C of dryings
24h, then be ground to below 100 mesh.24h being impregnated with the new 1mol/L sulfuric acid solution for preparing, is then filtered to remove excessive sulphuric acid
Solution, and 24h is dry at 105 DEG C.Gained solid is placed in quartz ampoule under the conditions of logical oxygen after 700 DEG C of roasting 3h, is answered
Mould assembly multifunctional solid acid catalyst SO4 2-/TiO2-ZrO2, bottle after cooling, be placed in standby in exsiccator.
Embodiment 3
By certain mass Ce (NO3)3·6H2O and ZrOCl2·8H2O is dissolved in 1000 milliliters of deionized water, to be dissolved after
Strong aqua ammonia being slowly added dropwise under stirring as precipitant, adjusts solution ph to 8～9, obtain stannum-zirconium hydroxide and sink
Form sediment, room temperature is aged 24h.After the completion of ageing, precipitation is washed with deionized, sucking filtration, until no Cl-Exist.By precipitate 105
DEG C 24h is dry, then be ground to below 100 mesh.24h being impregnated with the new 1mol/L sulfuric acid solution for preparing, is then filtered to remove excess
Sulfuric acid solution, and dry 24h at 105 DEG C.Gained 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 after cooling, be placed in standby in exsiccator.
Embodiment 4
By certain mass Co (NO3)2·6H2O and ZrOCl2·8H2O is dissolved in 1000 milliliters of deionized water, to be dissolved after
Strong aqua ammonia being slowly added dropwise under stirring as precipitant, adjusts solution ph to 8～9, obtain stannum-zirconium hydroxide and sink
Form sediment, room temperature is aged 24h.After the completion of ageing, precipitation is washed with deionized, sucking filtration, until no Cl-Exist.By precipitate 105
DEG C 24h is dry, then be ground to below 100 mesh.24h being impregnated with the new 1mol/L sulfuric acid solution for preparing, is then filtered to remove excess
Sulfuric acid solution, and dry 24h at 105 DEG C.Gained 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 after cooling, be placed in standby in exsiccator.
Embodiment 5
By inert carrier gas N2Fixed bed reaction pipe is passed into constant flow rate 30ml/min, while 4.0g mol ratio is 1:
5 acidification oils are pumped into added with 5.0g composite multi-functional solid acid catalyst SO as 3ml/h with constant flow rate with methyl alcohol mixed liquor4 2-/
SnO2-ZrO2Fixed bed reaction pipe in, in 350 DEG C of temperature, carrier gas nitrogen 40mL/min, under condition of normal pressure, carry out catalytic pyrolysiss,
Cracking oil vapour produced by last sequentially passes through 10 DEG C of condensing tubes, 0 DEG C of ice bath groove, prepared product after -220 DEG C of liquid nitrogen gradient freezings
Thing is mainly fatty acid methyl ester, and in gained product liquid, oil-phase product yield is 38.48%, water-phase product yield 6.49%.Oil
Phase product acid number is reduced to 38.64mgKOH/g by the 148.89mgKOH/g of original acidification oil.
Embodiment 6
By inert carrier gas N2Fixed bed reaction pipe is passed into constant flow rate 30ml/min, while 4.0g mol ratio is 1:
5 acidification oils are pumped into added with 5.0g composite multi-functional solid acid catalyst SO as 3ml/h with constant flow rate with methyl alcohol mixed liquor4 2-/
TiO2-ZrO2Fixed bed reaction pipe in, in 350 DEG C of temperature, carrier gas nitrogen 40mL/min, under condition of normal pressure, carry out catalytic pyrolysiss,
Cracking oil vapour produced by last sequentially passes through 10 DEG C of condensing tubes, 0 DEG C of ice bath groove, prepared product after -220 DEG C of liquid nitrogen gradient freezings
Thing is mainly rich hydrocarbon fuel oil, and in gained product liquid, oil-phase product yield is 52.02%, water-phase product yield 6.66%.Oil phase
Product acid number is reduced to 3.84mgKOH/g by the 148.89mgKOH/g of original acidification oil.
Embodiment 7
By inert carrier gas N2Fixed bed reaction pipe is passed into constant flow rate 30ml/min, while 4.0g mol ratio is 1:
5 acidification oils are pumped into added with 5.0g composite multi-functional solid acid catalyst SO as 3ml/h with constant flow rate with methyl alcohol mixed liquor4 2-/
Ce2O3-ZrO2Fixed bed reaction pipe in, in 350 DEG C of temperature, carrier gas nitrogen 40mL/min, carry out catalysis under condition of normal pressure and split
Solution, last produced cracking oil vapour sequentially passes through 10 DEG C of condensing tubes, 0 DEG C of ice bath groove, system after -220 DEG C of liquid nitrogen gradient freezings
Obtain product and fatty acid methyl ester is mainly, in gained product liquid, oil-phase product yield is 73.54%, water-phase product yield
4.04%.Oil-phase product acid number is reduced to 86.99mgKOH/g by the 148.89mgKOH/g of original acidification oil.
Embodiment 8
By inert carrier gas N2Fixed bed reaction pipe is passed into constant flow rate 30ml/min, while 4.0g mol ratio is 1:
5 acidification oils are pumped into added with 5.0g composite multi-functional solid acid catalyst SO as 3ml/h with constant flow rate with methyl alcohol mixed liquor4 2-/
CoO-ZrO2Fixed bed reaction pipe in, in 350 DEG C of temperature, carrier gas nitrogen 40mL/min, under condition of normal pressure, carry out catalytic pyrolysiss,
Cracking oil vapour produced by last sequentially passes through 10 DEG C of condensing tubes, 0 DEG C of ice bath groove, prepared product after -220 DEG C of liquid nitrogen gradient freezings
Thing is mainly fatty acid methyl ester, and in gained product liquid, oil-phase product yield is 73.54%, water-phase product yield 4.04%.Oil
Phase product acid number is reduced to 80.02mgKOH/g by the 148.89mgKOH/g of original acidification oil.
Embodiment 9
By inert carrier gas N2Fixed bed reaction pipe is passed into constant flow rate 30ml/min, while 4.0g mol ratio is 1:
5 acidification oils are pumped into added with 5.0g composite multi-functional solid acid catalyst SO as 3ml/h with constant flow rate with methyl alcohol mixed liquor4 2-/
TiO2-ZrO2Fixed bed reaction pipe in, in 300 DEG C of temperature, carrier gas nitrogen 40mL/min, under condition of normal pressure, carry out catalytic pyrolysiss,
Cracking oil vapour produced by last sequentially passes through 10 DEG C of condensing tubes, 0 DEG C of ice bath groove, prepared product after -220 DEG C of liquid nitrogen gradient freezings
Thing is mainly fatty acid methyl ester, and in gained product liquid, oil-phase product yield is 56.25%, water-phase product yield 4.23%.Oil
Phase product acid number is reduced to 21.78mgKOH/g by the 148.89mgKOH/g of original acidification oil.
Embodiment 10
By inert carrier gas N2Fixed bed reaction pipe is passed into constant flow rate 30ml/min, while 4.0g mol ratio is 1:
5 acidification oils are pumped into added with 5.0g composite multi-functional solid acid catalyst SO as 3ml/h with constant flow rate with methyl alcohol mixed liquor4 2-/
TiO2-ZrO2Fixed bed reaction pipe in, in 400 DEG C of temperature, carrier gas nitrogen 40mL/min, under condition of normal pressure, carry out catalytic pyrolysiss,
Cracking oil vapour produced by last sequentially passes through 10 DEG C of condensing tubes, 0 DEG C of ice bath groove, prepared product after -220 DEG C of liquid nitrogen gradient freezings
Thing is mainly based on rich hydrocarbon fuel oil and hydrocarbon product, and in gained product liquid, oil-phase product yield is that 65.85%, water-phase product is obtained
Rate 7.73%.Oil-phase product acid number is reduced to 7.05mgKOH/g by the 148.89mgKOH/g of original acidification oil.
Embodiment 11
By inert carrier gas N2Fixed bed reaction pipe is passed into constant flow rate 30ml/min, while 4.0g mol ratio is 1:
5 acidification oils are pumped into added with 5.0g composite multi-functional solid acid catalyst SO as 3ml/h with constant flow rate with methyl alcohol mixed liquor4 2-/
TiO2-ZrO2Fixed bed reaction pipe in, in 450 DEG C of temperature, carrier gas nitrogen 40mL/min, under condition of normal pressure, carry out catalytic pyrolysiss,
Cracking oil vapour produced by last sequentially passes through 10 DEG C of condensing tubes, 0 DEG C of ice bath groove, prepared product after -220 DEG C of liquid nitrogen gradient freezings
Thing is mainly rich hydrocarbon fuel oil and product is based on aromatic hydrocarbons, and in gained product liquid, oil-phase product yield is 44.36%, water-phase product
Yield 2.02%.Oil-phase product acid number is reduced to 6.03mgKOH/g by the 148.89mgKOH/g of original acidification oil.
Embodiment 12
By inert carrier gas N2Fixed bed reaction pipe is passed into constant flow rate 30ml/min, while 4.0g mol ratio is 1:
5 acidification oils are pumped into added with 5.0g composite multi-functional solid acid catalyst SO as 3ml/h with constant flow rate with methyl alcohol mixed liquor4 2-/
TiO2-ZrO2Fixed bed reaction pipe in, in 500 DEG C of temperature, carrier gas nitrogen 40mL/min, under condition of normal pressure, carry out catalytic pyrolysiss,
Cracking oil vapour produced by last sequentially passes through 10 DEG C of condensing tubes, 0 DEG C of ice bath groove, prepared product after -220 DEG C of liquid nitrogen gradient freezings
Thing is mainly rich hydrocarbon fuel oil and product is based on aromatic hydrocarbons, and in gained product liquid, oil-phase product yield is 30.87%, water-phase product
Yield 7.41%.Oil-phase product acid number is reduced to 6.03mgKOH/g by the 148.89mgKOH/g of original acidification oil.
Embodiment 13
By inert carrier gas N2Fixed bed reaction pipe is passed into constant flow rate 30ml/min, while by appropriate for 4.0g pretreatment
Cortex jatrophae fruit expressed oil afterwards, is directly pumped into added with 5.0g composite multi-functional solid acid catalysis with constant flow rate as 3ml/h
Agent SO4 2-/TiO2-ZrO2Fixed bed reaction pipe in, in 400 DEG C of temperature, carrier gas nitrogen 40mL/min, urged under condition of normal pressure
Change cracking, last produced cracking oil vapour sequentially passes through 10 DEG C of condensing tubes, 0 DEG C of ice bath groove, -220 DEG C of liquid nitrogen gradient freezings
Product is obtained afterwards rich hydrocarbon fuel oil is mainly, in gained product liquid, oil-phase product yield is 70.72%, almost without water-phase product.
Biomass carbon yield is 6.35%, and gas yield is 22.93%
Embodiment 14
By inert carrier gas N2Fixed bed reaction pipe is passed into constant flow rate 30ml/min, while by appropriate for 4.0g pretreatment
Rubber seed expressed oil afterwards, is directly pumped into added with 5.0g composite multi-functional solid acid catalyst with constant flow rate as 3ml/h
SO4 2-/TiO2-ZrO2Fixed bed reaction pipe in, in 400 DEG C of temperature, carrier gas nitrogen 40mL/min, be catalyzed under condition of normal pressure
Cracking, last produced cracking oil vapour sequentially passes through i0 DEG C of condensing tube, and 0 DEG C of ice bath groove, after -220 DEG C of liquid nitrogen gradient freezings
Prepared product is mainly rich hydrocarbon fuel oil, and in gained product liquid, oil-phase product yield is 69.85%, almost without water-phase product.Raw
Material charcoal yield is 8.15%, and gas yield is 22.00%.Oil-phase product acid number is by the 22.96mgKOH/ of original rubber seed oil
G, is reduced to 5.46mgKOH/g.
Embodiment 15
By inert carrier gas N2Fixed bed reaction pipe is passed into constant flow rate 30ml/min, while by appropriate for 4.0g pretreatment
Oleum Verniciae fordii afterwards, is directly pumped into added with 5.0g composite multi-functional solid acid catalyst SO with constant flow rate as 3ml/h4 2-/TiO2-
ZrO2Fixed bed reaction pipe in, in 400 DEG C of temperature, carrier gas nitrogen 40mL/min, carry out catalytic pyrolysiss under condition of normal pressure, finally
Produced cracking oil vapour sequentially passes through 10 DEG C of condensing tubes, 0 DEG C of ice bath groove, prepared product master after -220 DEG C of liquid nitrogen gradient freezings
Will be for rich hydrocarbon fuel oil and product based on aromatic hydrocarbons, in gained product liquid, oil-phase product yield is 69.13%, almost anhydrous mutually to produce
Thing.Biomass carbon yield is 7.68%, and gas yield is 23.19%.
Embodiment 16
By inert carrier gas N2Fixed bed reaction pipe is passed into constant flow rate 30ml/min, while by appropriate for 4.0g pretreatment
Waste oil afterwards, is directly pumped into added with 5.0g composite multi-functional solid acid catalyst SO with constant flow rate as 3ml/h4 2-/
TiO2-ZrO2Fixed bed reaction pipe in, in 400 DEG C of temperature, carrier gas nitrogen 40mL/min, under condition of normal pressure, carry out catalytic pyrolysiss,
Cracking oil vapour produced by last sequentially passes through 10 DEG C of condensing tubes, 0 DEG C of ice bath groove, prepared product after -220 DEG C of liquid nitrogen gradient freezings
Thing is mainly rich hydrocarbon fuel oil, and in gained product liquid, oil-phase product yield is 64.65%, almost without water-phase product.Biomass carbon
Yield is 7.44%, and gas yield is 27.91%.Oil-phase product acid number is reduced by the 99.11mgKOH/g of original rubber seed oil
For 4.54mgKOH/g.
Every technical staff's notice：Although the present invention is described according to above-mentioned specific embodiment, the present invention
Invention thought be not limited to that invention, the repacking of any utilization inventive concept, will all include this patent protection of the patent right
In the range of.
Claims (8)
1. a kind of preparation method of renewable richness hydrocarbon liquid fuel, comprises the following steps：
(1) in the presence of a inert carrier gas, by waste grease raw material after preheating with certain proportion methyl alcohol mixed liquor to set flow pump
Enter to be pre-loaded with the composite multi-functional solid acid catalyst reactor of 1～15g, 200～600 DEG C of reaction temperature, normal pressure bar
Catalytic pyrolysiss are carried out under part；
(2) produced cracking steam in step (1) is collected after gradient freezing and obtains product i.e. renewable richness hydrocarbon liquid
Fuel.
2. according to a kind of preparation method of renewable richness hydrocarbon liquid fuel of claim 1, it is characterised in that described in step (1)
Waste grease raw material includes inedible woody oils and fatss, expired food oil, acidification oil, waste oil, food and drink abandoned oil, microalgae
Oils and fatss etc..
3. according to a kind of preparation method of renewable richness hydrocarbon liquid fuel of claim 1, it is characterised in that described in step (1)
Reactor includes fixed-bed reactor, confined reaction kettle device, fluidized bed reaction.
4. according to a kind of preparation method of renewable richness hydrocarbon liquid fuel of claim 1, it is characterised in that described in step (1)
Inert carrier gas is N2, CO2, in He, Ar one or more.
5. according to a kind of preparation method of renewable richness hydrocarbon liquid fuel of claim 1, it is characterised in that described in step (1)
Catalyst is composite multi-functional solid acid.
6. according to a kind of preparation method of renewable richness hydrocarbon liquid fuel of claim 1, it is characterised in that described in step (1)
Composite solid acid is the compound of two or more metallic elements in IIA, IIIA, IVA, IIB, IVB, VIB, VIIB, VIII
SO is loaded on oxide4 2-.
7. according to a kind of preparation method of renewable richness hydrocarbon liquid fuel of claim 1, it is characterised in that described in step (2)
Gradient freezing be through 10 DEG C of condensing tubes, 0 DEG C of ice bath groove, -220 DEG C of liquid nitrogen three-level gradient freezings.
8. according to a kind of preparation method of renewable richness hydrocarbon liquid fuel of claim 1, it is characterised in that described in step (2)
Catalytic pyrolysiss gradient freezing is obtained the mixture of the hydro carbons such as the alkane, alkene, aromatic hydrocarbons that product is different carbon numbers 6～24.
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| CN201610402123.7A CN106433999B (en) | 2016-06-03 | 2016-06-03 | A kind of preparation method of renewable hydrocarbon-rich liquid fuel |
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| CN201610402123.7A CN106433999B (en) | 2016-06-03 | 2016-06-03 | A kind of preparation method of renewable hydrocarbon-rich liquid fuel |
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| CN106433999B CN106433999B (en) | 2019-11-15 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108640822A (en) * | 2018-04-25 | 2018-10-12 | 铜仁学院 | The preparation method and 4- vinyl guaiacols of 4- vinyl guaiacols |
| 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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| 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 |
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| 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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| 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 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108640822A (en) * | 2018-04-25 | 2018-10-12 | 铜仁学院 | The preparation method and 4- vinyl guaiacols of 4- vinyl guaiacols |
| 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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