CN104560225B - A kind of biomass produce the method for high-quality oil fuel - Google Patents
A kind of biomass produce the method for high-quality oil fuel Download PDFInfo
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Abstract
The invention discloses a kind of method that biomass produce high-quality oil fuel, comprise following content: biomass material, microwave additive and acidic solution are mixed, first microwave hydrolysis process is carried out, carry out microwave dehydration process again, then the biomass after dehydration are carried out microwave-heating, the volatiles generated uses multi-stage condensing to reclaim, solid-liquid separation, obtain bio oil, bio oil, again through etherification reaction, obtains being rich in furan alcohol ether fuel oil.The oil fuel that the method obtains not only yield is high, and component is simple, thermal value is high, stability in storage is good, is suitable as petrol and diesel oil or its addO-on therapy.
Description
Technical field
The present invention relates to a kind of method that biomass produce high-quality oil fuel.
Background technology
Biomass source is extensive, rich reserves, cheap and renewable, and the CO2 emissions utilizing process to produce is zero, environmental friendliness, is a kind of renewable energy source of environmental protection.From the long-term consideration of energy security, the biofuel utilizing the biomass such as lignocellulose to carry out production high-quality alleviates even to replace the effective way that fossil energy is under-supply, but be also faced with lot of challenges simultaneously.The how effective exploitation problem that utilizes this resource to become people can not to get around.
Biomass pyrolytic can realize low energy densities biomass material and be converted into high heating value liquid fuel, but at present the biomass crude oil water content that obtains of biomass pyrolytic is large, oxygen level is high, acidity is strong, viscosity is large, the calorific value comparatively low and poor stability of fossil oil, directly can not be used as vehicle fuel.In order to improve the quality of biomass pyrolysis oil, good try has been carried out in much research.On the one hand from biomass pyrolysis process, obtain by the method for directional catalyzing pyrolysis the bio-oil that certain one or several component is dominant, and then reach and simplify bio-oil components object.CN100999676A, CN100999677A and WO2010/033512 individually disclose the method that hydroxyacetone, furfural and methoxyl group furans ethanol are rich in the preparation of biomass microwave catalytic pyrolysis, but the bio oil yield that these methods obtain is lower, and water content is higher, add product separation purification difficulty.On the other hand from the refining of bio-oil and process for upgrading, reached by shortening or catalytic pyrolysis and reduce oxygen level and ratio of carbon-hydrogen, improve calorific value, the object of stability.The former uses hydrogen at elevated pressures, with the form of water or carbonic acid gas, deoxidation is removed to the unsaturated link(age) hydrogenating reduction in bio oil, bio oil or its steam reforming are hydro carbons by the latter at ambient pressure, with the form of water or carbonic acid gas or carbon monoxide, oxygen is removed equally, reach and reduce oxygen level and ratio of carbon-hydrogen, improve calorific value, the object of stability.But most research is by the object location of bio oil upgrading in the oxygen level reducing oil, but what consume that a large amount of hydrogen obtains is but only the water of the non-energy, the practical application of so high upgrading cost impact.
If the upgrading of bio oil with stable and inflammable oxygen-bearing organic matter for target, as alcohol, ether, ester etc., both can reach the object promoting bio oil grade, and can reduce again expensive deoxidation cost, promote the economy of bio oil process for upgrading.Ethers molecule has been widely used as vehicle fuel or additive, and methyl tertiary butyl ether, tert-amyl ether, diisopropyl ether, Ethyl Tertisry Butyl Ether and dme are all used as petrol and diesel oil octane promoter.Therefore, boundless market outlook will be had from the petrol and diesel oil octane promoter of biomass Development of Novel.
WO2009/141166 reports furfural or 5-alkoxymethylfurfural can be converted into furan alkyls alcohol ether under hydrogenation catalyst and the simultaneous condition of an acidic catalyst, but there is expensive raw material price and obtain difficult problem.WO2009/030508, WO2007/104515 and WO2009/030511 are respectively openly containing C
5and C
6glycogen material and alcohol react in the presence of acidic and generate furfural and 5-alkoxymethylfurfural, and then hydrogenation etherificate changes furan alkyls alcohol ether into, but the selectivity of target product is poor, and step is various, complex process, and energy consumption is high.
CN102442982A discloses a kind of method being prepared furyl dimethyl carbinol dialkyl ether by sugar, under an acidic catalyst and the simultaneous condition of hydrogenation catalyst, adopt single stage method to complete sugared dehydration, hydrogenation, etherificate, prepare corresponding furyl ethers product, but product yield is less than 40%.
Summary of the invention
Not enough for prior art, the invention provides a kind of method that biomass produce high-quality oil fuel.The oil fuel that the method obtains not only yield is high, and component is simple, thermal value is high, stability in storage is good, is suitable as petrol and diesel oil or its addO-on therapy.
Biomass of the present invention produce the method for high-quality oil fuel, comprise following content: biomass material, microwave additive and acidic solution are mixed, first microwave hydrolysis process is carried out, carry out microwave dehydration process again, then the biomass after dehydration are carried out microwave-heating, the volatiles generated uses multi-stage condensing to reclaim, solid-liquid separation, obtain bio oil, bio oil, again through etherification reaction, obtains product.
In the inventive method, microwave hydrolysis treatment condition are: treatment temp is 80 ~ 120 DEG C, and the treatment time is 5 ~ 30 minutes, and Microwave Power Density is 1 × 10
5~ 3 × 10
5w/m
3.
In the inventive method, microwave dehydration treatment condition are: treatment temp is 140 ~ 220 DEG C, and the treatment time is 5 ~ 15 minutes, and this process power density is 1 × 10
5~ 3 × 10
5w/m
3.
In the inventive method, microwave pyrolytic process is as follows: first 350 ~ 450 DEG C of pyrolysis 4 ~ 12 minutes, and be warming up to 500 ~ 600 DEG C of pyrolysis to not having gas to produce, wherein Microwave Power Density is 4 × 10
5~ 10 × 10
5w/m
3.
In the inventive method, whole reaction process is carried out in microwave-heating reactor, and keep negative pressure state, reaction pressure is 0.01 ~ 0.1MPa.
In the inventive method, described biomass material is any biomass containing lignocellulose such as maize straw, rice husk, straw, wooden unit, leaf or branch.Raw material shape can be the biomass comprising any shapes such as sheet material, circle, cylinder, taper, rectangular parallelepiped, and raw material maximum direction size is no more than 20mm, preferably 0.2 ~ 10mm, more preferably 0.5 ~ 5mm.
In the inventive method, described acidic solution refers to anyly have release [H
+] medium, comprise the protonic acids such as sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, carbonic acid, boric acid, hydrofluoric acid, Hydrogen bromide, perchloric acid, organic acid or its acid anhydrides such as formic acid, acetic acid, propionic acid, oxalic acid, succinic acid, hexanodioic acid, citric acid, one or more of the acidic salt solution such as metal halide, acid salt, acidic solution concentration 0.5wt% ~ 5wt%.
In the inventive method, the mass ratio of described biomass material, microwave additive and acidic solution is 1:0.1 ~ 2:0.1 ~ 0.5.
In the inventive method, described microwave additive, by mass percentage, comprises following component: the metal oxide 50% ~ 95% of microwave absorbing, and preferably 70% ~ 90%, the oxide compound 5 ~ 50% of non-microwave absorbing; Wherein the metal oxide of microwave absorbing character be selected from IIIB, IVB and IIIA can not valence variation element and be no more than in two valence variation element oxide compounds one or more, comprise Al
2o
3,tiO
2,la
2o
3,y
2o
3or ZrO
2deng one or more in oxide compound; The oxide compound of non-microwave absorbing character is selected from SiO
2, CaO or Na
2one or more in O etc.; Wherein the granularity of microwave additive is 0.1 ~ 10mm, preferably 0.5 ~ 5mm.
In the inventive method, the preparation method of described microwave additive, comprises following content: by the oxide compound of the metal oxide of microwave absorbing, non-microwave absorbing and water mixing, form slurries, then carry out wet-milling, then roasting, shaping, sintering, be cooled to room temperature, obtain microwave additive; Wherein said wet-milling process adopts the equipment such as ball mill, wet wheeling machine to carry out, and the wet-milling time is 6 ~ 24 hours, preferably 12 ~ 20 hours; Wherein can add the auxiliary agents such as ethanol, methyl alcohol, Virahol, acetone in slurries; Described roasting condition is: roasting 2 ~ 4 hours at 550 ~ 650 DEG C; Condition of molding is: pressure is 120 ~ 200MPa, and the time is 5 ~ 10 minutes; Sintering condition is: 1000 ~ 1400 DEG C sinter 1 ~ 4 hour.
In the inventive method, described solid-liquid separation comprises any methods realizing solid-liquid separation such as sedimentation, filtration, suction filtration, extruding or cyclonic separation.
In the inventive method, described etherification reaction process is: in bio oil, add 5 ~ 10 times of volume dehydrated alcohols, then add catalyst for etherification, at nitrogen pressure 0.1 ~ 4MPa, temperature 100 ~ 200 DEG C, reacts 1 ~ 12 hour; The mass ratio of wherein said catalyst for etherification and bio oil is 0.01 ~ 1:1.
Wherein, described catalyst for etherification is load-type solid acid catalyst, and active ingredient is ZrO
2, TiO
2, Al
2o
3deng metal oxide and sulfuric acid modified amphoteric metal oxide compound or composite oxides, be selected from SO
4 2-/ SnO
2, SO
4 2-/ SiO
2, SO
4 2-/ ZrO
2, SO
4 2-/ TiO
2or SO
4 2-/ Al
2o
3one or more; Carrier comprises Al
2o
3, in ZSM-5, ZSM-23, ZSM-48, MCM-41, SBA-15 and sulfonated gac one or more; Described support of the catalyst also can directly use as solid acid catalyst.The catalyzer of described supported solid acid can adopt this area ordinary method preparation.
The inventive method compared with prior art, has the following advantages:
(1) microwave additive assists biomass microwave pyrolysis, its normal temperature microwave field is utilized not absorb microwave and the feature of the specific absorption raising that heats up, can alleviate and even avoid traditional biomass microwave-heating system to pursue quick heating merely and cause the too high phenomenon causing volatile matter generation second pyrolysis of local " focus " local temperature, under microwave additive high temperature, suitable microwave absorption capacity also ensures instant the shifting out of volatile matter simultaneously, and is not susceptible to being infected and lysed by viruses or condensation.
(2) microwave additive assists the intensification behavior of biomass microwave pyrolysis to meet the requirement of bio liquid pyrolysis product maximize yields.Under the same conditions, the biomass system itself adding microwave additive can be rapidly heated 300 ~ 400 DEG C and maintain for some time, is then just warmed up to design temperature and continues pyrolysis.This body intensification behavior not only eliminates microwave in the poor trouble of middle high temperature temperature control, and achieve the classification pyrolysis of biomass chemical constitution to a certain extent, namely Mierocrystalline cellulose and hemicellulose are 300 ~ 400 DEG C of abundant pyrolysis, and xylogen then carries out extensive pyrolysis near 600 DEG C.
(3) traditional biomass microwave absorbs pyrolysis systems and usually can be rapidly heated target temperature, but due to the lag-effect of biomass pyrolytic heat release, cause temperature constantly to rise, successive processes constantly can carry out control temperature by switch microwave source.Once turn off microwave source, biomass will lose microwave heating instantaneously, and this can cause the excessive pyrolysis of part biological matter in successive processes, and part biological matter exists " half-cooked " phenomenon.The present invention makes it maintain for some time at 300 ~ 400 DEG C by the regulation and control of microwave additive wave-sucking performance, then just target temperature can be warmed up to, make biomass continuous microwave cracking before 400 DEG C, avoid the problem constantly opening and closing microwave, then rise to higher temperature and carry out deep pyrolytic, be conducive to the continuous operation of microwave-heating.
(4) microwave additive add the problem that acid catalysis pyrolysis in the past can be avoided to generate more biological burnt and gas, bio oil yield is high, quality good.
(5) after adopting the first acid hydrolysis of microwave, the method for pyrolysis can make Mierocrystalline cellulose and hemicellulose in biomass, through acid hydrolysis, depolymerization to a certain degree occur, obtain having the fibre fractionation of comparatively low polymerization degree (lower molecular weight), activation wood fibre, reduce the molecular weight of biofuel oil, obtain the bio oil being rich in furan alcohol and levoglucosenone.
(6) in bio oil etherification procedure, levoglucosenone is first converted into hydroxymethylfurfural by acidic etherification catalyst, then makes furan alcohol and the further etherificate of hydroxymethylfurfural obtain high-quality oil fuel.
Accompanying drawing explanation
Fig. 1 is the biomass heating curve that with the addition of microwave additive TC of comparative example 1 ~ 2 and embodiment 2 ~ 5.
Wherein, the A ~ B in comparative example 1 ~ 2 corresponding diagram 1 curve, the C ~ F in embodiment 2 ~ 5 corresponding diagram 1 curve.
Embodiment
Further illustrate process and the effect of the inventive method below by embodiment, but therefore do not limit the present invention.Percentage composition involved is below mass percentage.Gas chromatography mass spectrometry chromatogram is adopted to analyze bio oil and fuel oil composition in the inventive method.
The preparation method of load-type solid acid catalyst of the present invention is as follows: by the nitrate of metal oxide or other soluble salt wiring solution-formings (0.2mol/L), precipitation of hydroxide is separated out with ammoniacal liquor, add support of the catalyst fully to mix (in every 15ml salts solution, adding 1g carrier), after aging 24 hours through filtering, washing, dry, grinding, 550 DEG C of roastings 3 hours; The catalyzer of sulfation modification then needs above-mentioned catalyzer before calcination, use 1mol/L concentration sulphuric acid solution impregnation 24 hours, drier, roasting.
Embodiment 1
First take a certain amount of silicon sol and be diluted with water to 5% hydrosol solution, then in silicon sol solution, adding а-Al
2o
3powder (diameter is less than 1 μm), ZrO
2powder (diameter is less than 0.5 μm), then add ethanol in proper amount, put into ball mill and carry out wet-milling.Carry out drying through wet-milling after 24 hours, cross the roasting 2 hours at 600 DEG C of the powder after 60 mesh sieves, then carry out shaping as requested.Molding blank 1200 DEG C of sintering in atmospheric environment slowly cooled to room temperature with furnace temperature after 2 hours.Prepare two kinds of microwave additive TC-1 and TC-2 respectively according to the difference of raw material proportion of composing, wherein TC-1 consists of 65%Al
2o
3, 35%SiO
2, 5%ZrO
2, TC-2 consists of 85%Al
2o
3, 10%SiO
2, 5%ZrO
2.
Embodiment 2
By 100g wood chip (5mm), TC-1(5mm) and 0.5% phosphoric acid solution mix according to mass ratio 1:0.1:0.1 and be placed in microwave-heating reactor, first 120 DEG C of microwave hydrolysis process 5 minutes, then be warming up to 140 DEG C to dewater, time is 15 minutes, and whole hydrolysis and dehydration power density are 1 × 10
5w/m
3.Modulating Power 4 × 10
5w/m
3, and by the biomass of above-mentioned dehydration 350 DEG C of pyrolysis 4 minutes, and then be warming up to 500 DEG C of pyrolysis to not having gas to produce, the volatiles generated uses multi-stage condensing carry out reclaiming and carry out solid-liquid separation, obtain bio oil 38g, wherein furans content 24.1%, contents of saccharide 9.7%.
Embodiment 3
By 100g wood chip (5mm), TC-2(5mm) and 5% phosphoric acid solution mix according to mass ratio 1:1:0.3 and be placed in microwave-heating reactor, first 80 DEG C of microwave hydrolysis process 30 minutes, then be warming up to 160 DEG C to dewater, time is 10 minutes, and whole hydrolysis and dehydration power density are 2 × 10
5w/m
3.Modulating Power to 4 × 10
5w/m
3and by the biomass of above-mentioned dehydration 400 DEG C of pyrolysis 12 minutes, and then be warming up to 600 DEG C of pyrolysis to not having gas to produce, the volatiles generated uses multi-stage condensing carry out reclaiming and carry out solid-liquid separation, obtain bio oil 58g, wherein furans content 59.4%, contents of saccharide 19.6%.
Embodiment 4
By 100g wood chip (5mm), TC-2(5mm) and 5% phosphoric acid solution mix according to mass ratio 1:2:0.3 and be placed in microwave-heating reactor, first 80 DEG C of microwave hydrolysis process 30 minutes, then be warming up to 160 DEG C to dewater, time is 10 minutes, and whole hydrolysis and dehydration power density are 2 × 10
5w/m
3.Modulating Power to 4 × 10
5w/m
3and by the biomass of above-mentioned dehydration 450 DEG C of pyrolysis 12 minutes, and then be warming up to 600 DEG C of pyrolysis to not having gas to produce, the volatiles generated uses multi-stage condensing carry out reclaiming and carry out solid-liquid separation, obtain bio oil 56g, wherein furans content 56.7%, contents of saccharide 17.8%.
Embodiment 5
By 100g wood chip (5mm), TC-2(1mm) and 5% phosphoric acid solution mix according to mass ratio 1:0.75:0.3 and be placed in microwave-heating reactor, first 80 DEG C of microwave hydrolysis process 30 minutes, then be warming up to 160 DEG C to dewater, time is 10 minutes, and whole hydrolysis and dehydration power density are 2 × 10
5w/m
3.Modulating Power to 4 × 10
5w/m
3and by the biomass of above-mentioned dehydration 400 DEG C of pyrolysis 12 minutes, and then be warming up to 600 DEG C of pyrolysis to not having gas to produce, the volatiles generated uses multi-stage condensing carry out reclaiming and carry out solid-liquid separation, obtain 64g bio oil, wherein furans content 60.2%, contents of saccharide 22.1%.
Embodiment 6
By 100g wood chip (5mm), TC-2(5mm) and 5% sulphuric acid soln mix according to mass ratio 1:1:0.5 and be placed in microwave-heating reactor, first 80 DEG C of microwave hydrolysis process 30 minutes, then be warming up to 160 DEG C to dewater, time is 10 minutes, and whole hydrolysis and dehydration power density are 2 × 10
5w/m
3.Modulating Power to 4 × 10
5w/m
3and by the biomass of above-mentioned dehydration 400 DEG C of pyrolysis 12 minutes, and then be warming up to 600 DEG C of pyrolysis to not having gas to produce, the volatiles generated uses multi-stage condensing carry out reclaiming and carry out solid-liquid separation, obtain bio oil 38g, wherein furans content 45.4%, contents of saccharide 10.8%.
Comparative example 1
100g wood chip (5mm) and 5% phosphoric acid solution mixed according to mass ratio 1:0.3 and dries, being then placed in microwave-heating reactor at 600 DEG C, 4 × 10
5w/m
3carry out pyrolysis, till question response process no longer includes gas generation, the volatiles generated uses multi-stage condensing carry out reclaiming and carry out solid-liquid separation, obtains the biofuel oil 41g not containing solid particulate, wherein furans content 34.5%, contents of saccharide 14.8%.
Comparative example 2
100g wood chip (5mm), biomass coke and 5% phosphoric acid solution are mixed according to mass ratio 1:0.1:0.3 and is placed in microwave-heating reactor, first microwave hydrolysis process 30 minutes at 80 DEG C, then rise to 160 DEG C to dewater, time is 10 minutes, whole hydrolysis and dehydration power 3 × 10
5w/m
3.Modulating Power to 4 × 10
5w/m
3and by the biomass of above-mentioned dehydration 400 DEG C of pyrolysis 4 minutes, and then be warming up to 600 DEG C of pyrolysis to not having gas to produce, the volatiles generated uses multi-stage condensing carry out reclaiming and carry out solid-liquid separation, obtain the biofuel oil 44g not containing solid particulate, wherein furans content 32.4%, contents of saccharide 8.5%.
Comparative example 3
100g wood chip (5mm) and 0.5% phosphoric acid solution are mixed according to mass ratio 1:0.1 and is placed in microwave-heating reactor, first 120 DEG C of microwave hydrolysis process 5 minutes, then be warming up to 140 DEG C to dewater, the time is 15 minutes, and whole hydrolysis and dehydration power density are 1 × 10
5w/m
3.Modulating Power 4 × 10
5w/m
3, and by the biomass of above-mentioned dehydration 350 DEG C of pyrolysis 4 minutes, and then be warming up to 500 DEG C of pyrolysis to not having gas to produce, the volatiles generated uses multi-stage condensing carry out reclaiming and carry out solid-liquid separation, obtain bio oil 35g, wherein furans content 22.9%, contents of saccharide 7.8%.
Embodiment 7
100ml dehydrated alcohol is added in the bio oil of 10g embodiment 5, add 2gZSM-5 again, be filled with nitrogen deoxygenation, start to carry out stirring reaction when temperature is raised to 120 DEG C, control nitrogen pressure 2MPa, etherification reaction are down to room temperature after 5 hours, Filtration of catalyst simultaneously, after product at reduced pressure distillation removing ethanol, namely obtain being rich in furan alcohol ether fuel product, concrete outcome is in table 1.
Embodiment 8
In the bio oil of 10g embodiment 5, add 100ml dehydrated alcohol, then add 2gTiO
2-SBA-15, be filled with nitrogen deoxygenation, start to carry out stirring reaction when temperature is raised to 140 DEG C, control nitrogen pressure 0.5MPa, etherification reaction were down to room temperature after 8 hours simultaneously, Filtration of catalyst, after product at reduced pressure distillation removing ethanol, namely obtain being rich in furan alcohol ether fuel product, concrete outcome is in table 1.
Embodiment 9
In the bio oil of 10g embodiment 5, add 100ml dehydrated alcohol, then add 2gZrO
2-MCM-41, be filled with nitrogen deoxygenation, start to carry out stirring reaction when temperature is raised to 160 DEG C, control nitrogen pressure 1MPa, etherification reaction were down to room temperature after 10 hours simultaneously, Filtration of catalyst, after product at reduced pressure distillation removing ethanol, namely obtain being rich in furan alcohol ether fuel product, concrete outcome is in table 1.
Embodiment 10
In the bio oil of 10g embodiment 5, add 100ml dehydrated alcohol, then add 2gSO
4 2-/ ZrO
2-SBA-15, is filled with nitrogen deoxygenation, starts to carry out stirring reaction when temperature is raised to 140 DEG C, control nitrogen pressure 1MPa, etherification reaction are down to room temperature after 6 hours, Filtration of catalyst simultaneously, after product at reduced pressure distillation removing ethanol, namely obtain being rich in furan alcohol ether fuel product, concrete outcome is in table 1.
Embodiment 11
In the bio oil of 10g embodiment 5, add 100ml dehydrated alcohol, then add 2gSO
4 2-/ ZrO
2-ZSM-5, is filled with nitrogen deoxygenation, starts to carry out stirring reaction when temperature is raised to 140 DEG C, control nitrogen pressure 1MPa, etherification reaction are down to room temperature after 5 hours, Filtration of catalyst simultaneously, after product at reduced pressure distillation removing ethanol, namely obtain being rich in furan alcohol ether fuel product, concrete outcome is in table 1.
Comparative example 3
In the bio oil of 10g comparative example 1, add 100ml dehydrated alcohol, then add 2gSO
4 2-/ ZrO
2-SBA-15, is filled with nitrogen deoxygenation, starts to carry out stirring reaction when temperature is raised to 140 DEG C, control nitrogen pressure 1MPa, etherification reaction are down to room temperature after 6 hours, Filtration of catalyst simultaneously, after product at reduced pressure distillation removing ethanol, namely obtain being rich in furan alcohol ether fuel product, concrete outcome is in table 1.
Comparative example 4
In the bio oil of 10g comparative example 2, add 100ml dehydrated alcohol, then add 2gSO
4 2-/ ZrO
2-SBA-15, is filled with nitrogen deoxygenation, starts to carry out stirring reaction when temperature is raised to 140 DEG C, control nitrogen pressure 1MPa, etherification reaction are down to room temperature after 6 hours, Filtration of catalyst simultaneously, after product at reduced pressure distillation removing ethanol, namely obtain being rich in furan alcohol ether fuel product, concrete outcome is in table 1.
Compositional analysis after table 1 bio oil etherificate.
In the inventive method, described microwave additive has unique heating curve, be different from the intensification behavior (see B in Fig. 1) that normally used microwave absorption rises to 1000 DEG C within a short period of time, under the same conditions, described microwave additive shows as two-part heating curve (see C ~ F in Fig. 1), namely be first raised to 300 DEG C fast, then maintain certain hour in 300 ~ 400 DEG C, then rise to higher temperature.
Claims (13)
1. biomass produce the method for high-quality oil fuel, it is characterized in that comprising following content: biomass material, microwave additive and acidic solution are mixed, first microwave hydrolysis process is carried out, carry out microwave dehydration process again, then the biomass after dehydration are carried out microwave-heating, the volatiles generated uses multi-stage condensing to reclaim, solid-liquid separation, obtain bio oil, bio oil, again through etherification reaction, obtains product; Described microwave additive, by mass percentage, comprises following component: the metal oxide 50% ~ 95% of microwave absorbing, the oxide compound 5 ~ 50% of non-microwave absorbing; Wherein the metal oxide of microwave absorbing character be in IIIB, IVB and IIIA can not valence variation element and be no more than in two valence variation element oxide compounds one or more, be selected from Al
2o
3, TiO
2, La
2o
3, Y
2o
3or ZrO
2one or more in oxide compound; The oxide compound of non-microwave absorbing character is selected from SiO
2, CaO or Na
2one or more in O; Wherein the granularity of microwave additive is 0.1 ~ 10mm.
2. in accordance with the method for claim 1, it is characterized in that: microwave hydrolysis treatment condition are: treatment temp is 80 ~ 120 DEG C, the treatment time is 5 ~ 30 minutes, and Microwave Power Density is 1 × 10
5~ 3 × 10
5w/m
3.
3. in accordance with the method for claim 1, it is characterized in that: microwave dehydration treatment condition are: treatment temp is 140 ~ 220 DEG C, the treatment time is 5 ~ 15 minutes, and this process power density is 1 × 10
5~ 3 × 10
5w/m
3.
4. in accordance with the method for claim 1, it is characterized in that: microwave pyrolytic process is as follows: first 350 ~ 450 DEG C of pyrolysis 4 ~ 12 minutes, be warming up to 500 ~ 600 DEG C of pyrolysis to not having gas to produce, wherein Microwave Power Density is 4 × 10
5~ 10 × 10
5w/m
3.
5. in accordance with the method for claim 1, it is characterized in that: whole reaction process is carried out in microwave-heating reactor, reaction pressure is 0.01 ~ 0.1MPa.
6. in accordance with the method for claim 1, it is characterized in that: described biomass material is the biomass containing lignocellulose, be selected from one or more in maize straw, rice husk, straw, wooden unit, leaf or branch; Raw material maximum direction size is no more than 20mm.
7. in accordance with the method for claim 1, it is characterized in that: described acidic solution refers to any medium with release [H+], be selected from sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, carbonic acid, boric acid, hydrofluoric acid, Hydrogen bromide, perchloric acid, in the acidic salt solution of the acid anhydrides of formic acid, acetic acid, propionic acid, oxalic acid, succinic acid, hexanodioic acid or citric acid and formic acid, acetic acid, propionic acid, oxalic acid, succinic acid, hexanodioic acid or citric acid, metal halide or acid salt one or more, acidic solution concentration 0.5wt% ~ 5wt%.
8. in accordance with the method for claim 1, it is characterized in that: the mass ratio of described biomass material, microwave additive and acidic solution is 1:0.1 ~ 2:0.1 ~ 0.5.
9. in accordance with the method for claim 1, it is characterized in that: the preparation method of described microwave additive, comprise following content: by the oxide compound of the metal oxide of microwave absorbing, non-microwave absorbing and water mixing, form slurries, then wet-milling is carried out, then roasting, shaping, sintering, be cooled to room temperature, obtain microwave additive.
10. in accordance with the method for claim 9, it is characterized in that: wherein said wet-milling process adopts ball mill or wet wheeling machine to carry out, and the wet-milling time is 6 ~ 24 hours; One or more auxiliary agents in ethanol, methyl alcohol, Virahol or acetone are added in slurries.
11. in accordance with the method for claim 9, it is characterized in that: described roasting condition is: roasting 2 ~ 4 hours at 550 ~ 650 DEG C; Condition of molding is: pressure is 120 ~ 200MPa, and the time is 5 ~ 10 minutes; Sintering condition is: 1000 ~ 1400 DEG C sinter 1 ~ 4 hour.
12. in accordance with the method for claim 9, it is characterized in that: described etherification reaction process is: in bio oil, add 5 ~ 10 times of volume dehydrated alcohols, add catalyst for etherification again, at nitrogen pressure 0.1 ~ 4MPa, temperature 100 ~ 200 DEG C, react 1 ~ 12 hour; The mass ratio of wherein said catalyst for etherification and bio oil is 0.01 ~ 1:1.
13. in accordance with the method for claim 12, it is characterized in that: described catalyst for etherification is load-type solid acid catalyst, and active ingredient is ZrO
2, TiO
2or Al
2o
3and sulfuric acid modified amphoteric metal oxide compound or composite oxides, be selected from SO
4 2-/ SnO
2, SO
4 2-/ SiO
2, SO
4 2-/ ZrO
2, SO
4 2-/ TiO
2or SO
4 2-/ Al
2o
3in one or more, carrier is Al
2o
3, in ZSM-5, ZSM-23, ZSM-48, MCM-41, SBA-15 and sulfonated gac one or more.
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| CN105199769A (en) * | 2015-10-16 | 2015-12-30 | 上海应用技术学院 | Method for preparing bio-oil efficiently |
| CN106221719A (en) * | 2016-08-04 | 2016-12-14 | 陈永林 | A kind of method utilizing biomass microwave pyrolysis preparation bio oil |
| CN108914096A (en) * | 2018-07-25 | 2018-11-30 | 芜湖昌菱金刚石工具有限公司 | A kind of preparation method of diamond surface cladding Ni-W-P metallization coating |
| CN109692690B (en) * | 2018-12-24 | 2020-08-25 | 华中科技大学 | Catalyst for producing levoglucosenone and preparation method thereof |
| CN111545242A (en) * | 2020-04-28 | 2020-08-18 | 东南大学 | Pre-coking oriented modified ZSM-5 molecular sieve for preparing oil by microwave-assisted heating and catalytic pyrolysis of biomass and preparation method thereof |
| CN114891529A (en) * | 2022-04-21 | 2022-08-12 | 南京昊绿生物科技有限公司 | Method for preparing high-quality bio-oil by catalyzing algae microwave hydrolysis through heterogeneous composite molecular sieve |
| CN114907875B (en) * | 2022-06-09 | 2023-08-15 | 武汉轻工大学 | Method for co-producing high-quality pyrolysis gas and biological oil by using biomass and polyolefin plastic |
| CN115608369B (en) * | 2022-11-08 | 2024-02-23 | 江西农业大学 | Preparation method and application of lanthanum ferrite perovskite type composite oxide |
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