CN104109563B - A kind of take biomass as the method that biogasoline prepared by raw material - Google Patents
A kind of take biomass as the method that biogasoline prepared by raw material Download PDFInfo
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- CN104109563B CN104109563B CN201410352807.1A CN201410352807A CN104109563B CN 104109563 B CN104109563 B CN 104109563B CN 201410352807 A CN201410352807 A CN 201410352807A CN 104109563 B CN104109563 B CN 104109563B
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- biogasoline
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- angelica lactone
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Abstract
The present invention relates to a kind of is raw material with biomass, is prepared the method for biogasoline by biomass by hydrolyzation, dehydration, polymerization, hydrogenation four step.Namely biomass are that the diluted acid of 0.1%-10% is hydrolyzed 5-240min and prepares levulinic acid when 140-220 DEG C by concentration; Levulinic acid in the liquid acid of 0.1-5%, or under acidic ion liquid or molecular sieve effect, reacts 60-180min Dehydration for angelica lactone when 130-180 DEG C; Angelica lactone under the mineral alkali effect of 0.1-5% in 60-160 DEG C time reaction 1-180min polymerization prepare angelica lactone polymkeric substance; Angelica lactone polymkeric substance is under the catalyst action of 0.1%-5%, and hydrogenation reaction 4-60h when 200-400 DEG C, obtains final product biogasoline.The method can increase substantially the utilization ratio of carbon, reduces Carbon emission, can reduce again the dependence to Nonrenewable resources such as oil.This legal system is short for biogasoline technical process, and reaction conditions is gentle, and product yield is high, superior product quality.
Description
Technical field
The invention belongs to biological gasoline novel energy preparation field, being specifically related to a kind of is raw material with biomass, and prepare levulinic acid by biomass by hydrolyzation, levulinic acid Dehydration is for angelica lactone, then angelica lactone polymkeric substance is prepared in polymerization, and the method for biogasoline is prepared in last hydrogenation of polymer deoxidation.
Background technology
In recent years, what adjoint world economy increased rapidly is the exhaustion day by day of fossil energy and going from bad to worse of environment for human survival.Due to the promotion of petrochemical industry economy, world economy is with unprecedented speed increment, but the energy dilemma brought thus and ecocrisis also highlight day by day.Calculate with current spending rate, the prospective oil that the earth has been verified only can maintain the demand of 40-60.Therefore, following fossil oil in short supply be the universe all must faced by reality.Meanwhile, all the increasing with year of irreversible gas concentration lwevel in air, global warming problem day by day serious, now the survival and development of the mankind in serious threat.Therefore, finding exploitation renewable energy source (sun power, Geothermal energy, hydraulic energy, wind energy, underground heat and biomass energy) and become the most urgent task, is that minimizing is to the dependence of non-renewable fossil oil and the inevitable choice realizing reduction of discharging and social sustainable development.But in numerous renewable energy sources, sun power, Geothermal energy, hydraulic energy, wind energy, underground heat all limit by certain regional condition.And biomass energy is by photosynthesis stabilizing carbon dioxide and water by plant, sun power is stored in plant with chemical energy form, be the class renewable resources that ready-made a, nature exists at most, distribution is the widest, therefore occupy an important position in its renewable energy source abroad.The exploitation of biomass energy and use, while reduction Carbon emission, can obtain steady sources, the substitute energy of supply security, and the dependence reduced fossil oil, be the clean fuel of generally acknowledging in the world, the renewable energy source of European Union more than 1/2 all carrys out authigenic material.
Common biomass-making is thermochemical treatment method for the method for liquid fuel, namely with heat effect by raw material normal pressure/pressurization and heat condition under obtain the intermediate product such as liquid or gas, obtain biological wet goods fuel or fuel dope by means such as intermediate treatment, FT synthesis, upgradings.Biological oil composition determines the shortcomings such as its calorific value is low, poor stability, needs to carry out hydrofining process to reduce its oxygen level and to improve calorific value to it.
By biomass-making for biogasoline, Substitute For Partial petroleum based fuels, can reduce the dependence to Nonrenewable resources such as oil, reduce CO
2the high-value-use approach of discharge, expansion biomass resource, has important practical significance and vast potential for future development.
Advantage of the present invention is as follows:
1, by discarded biomass for the preparation of biogasoline, the utilization ratio of carbon can be increased substantially, contribute to reducing Carbon emission, the living environment of the protection mankind;
2, by discarded biomass for the preparation of biogasoline, the dependence to Nonrenewable resources such as oil can be reduced, alleviate the present situation that china natural resources is in short supply, ensure economic Sustainable development;
3, by discarded biomass for the preparation of biogasoline, can turn waste into wealth, expand the higher value application approach of biomass resource;
4, the method have selected suitable catalyzer under relatively mild condition, achieves the conversion of biomass to the liquid fuel of high added value, has greatly saved energy consumption.
5, to prepare biogasoline technical process short for the method, and product yield is high, superior product quality.
Summary of the invention
The object of the present invention is to provide a kind of take biomass carbohydrates as the method that biogasoline prepared by raw material, and the method prepares biogasoline by biomass by hydrolyzation, dehydration, polymerization, hydrogenation four step rule.
It is raw material that the present invention proposes with biomass, prepares levulinic acid by biomass by hydrolyzation, and levulinic acid Dehydration is for angelica lactone, and angelica lactone polymkeric substance is prepared in angelica lactone polymerization, and biogasoline is prepared in the deoxidation of last angelica lactone hydrogenation of polymer.The wherein aqueous hydrochloric acid of the first step biomass by hydrolyzation used catalyst to be mass concentration be 0.1%-10%, hydrolysis material biomass comprise wood chip, bagasse, sawdust, Mierocrystalline cellulose, stalk, absorbent cotton, fructose, glucose, starch, its concentration is the 2%-10% of acid solution quality, reaction times is 5-240min, and temperature of reaction is 140-220 DEG C; The raw material of second step dehydration is the levulinic acid that the first step biomass by hydrolyzation produces, and the method that dehydration adopts is the method for catalyzed reaction isolation integral, and catalyzer used is phosphoric acid, sulfuric acid, hydrochloric acid liquid acid, or [DMIPA] [HSO
4], [(n-Bu-SO
3h) MIm] [HSO
4] acidic ion liquid or ZSM-5 molecular sieve, catalyst levels is the 0.1-5% of raw material levulinic acid quality, and the reaction times is 60-180min, and temperature of reaction is 130-180 DEG C; The raw material of the 3rd step polymerization is the standby angelica lactone of second step levulinic acid Dehydration, and the catalyzer that polymerization adopts is K
2cO
3, Na
2cO
3, NaHCO
3, Ca (OH)
2inorganic salt or mineral alkali, consumption is the 0.1-5% of raw material angelica lactone quality, and the reaction times is 1-180min, and temperature of reaction is 60-160 DEG C; The raw material of the 4th step hydrogenation is the angelica lactone polymkeric substance of the 3rd step angelica lactone polymerization preparation, the catalyzer that hydrogenation adopts is 10%Pd/C, 5%Pd/C, NiFeCr, NiMoAl, consumption is the 0.1-5% of polymerizable raw material amount, and the reaction times is 4-60h, and temperature of reaction is 200-400 DEG C.
Concrete operation step of the present invention is as follows:
(1) biomass starting material (comprising wood chip, bagasse, sawdust, Mierocrystalline cellulose, stalk, absorbent cotton, fructose, glucose or starch) is under the hydrochloric acid catalysis of 0.1%-10% in mass concentration in autoclave, when 140-220 DEG C, react 5-240min, obtain the raw material levulinic acid of second step dehydration;
(2) levulinic acid adopts the method for catalyzed reaction isolation integral, in phosphoric acid, sulfuric acid, the hydrochloric acid liquid acid of its quality 0.1-5%, or [DMIPA] [HSO
4], [(n-Bu-SO
3h) MIm] [HSO
4] under acidic ion liquid or ZSM-5 molecular sieve catalyst action, adopt the method for reaction distillation product and raw material to be separated, and derive reaction product, wherein temperature of reaction is 130-180 DEG C, reaction times is 60-180min, obtains the raw material angelica lactone of the 3rd step polymerization;
(3) the 3rd steps are by the K of angelica lactone at its quality 0.1-5%
2cO
3, Na
2cO
3, NaHCO
3, Ca (OH)
2under mineral alkali catalysis, when 60-160 DEG C, react 1-180min, obtain the raw material angelica lactone polymkeric substance of the 4th step dehydration;
(4) last angelica lactone polymkeric substance is under 10%Pd/C, 5%Pd/C, NiFeCr, NiMoAl catalyst action of its quality 0.1%-5%, and hydrogenation reaction 4-60h when 200-400 DEG C, obtains final product biogasoline.The mode of wherein reacting can be intermittent type or continous way.
Accompanying drawing explanation
Fig. 1 is the UPLC collection of illustrative plates of angelica lactone
Fig. 2 is the FT-IR collection of illustrative plates of angelica lactone
Fig. 3 is the UPLC collection of illustrative plates of angelica lactone polymkeric substance
Fig. 4 is the FT-IR collection of illustrative plates of angelica lactone polymkeric substance
Fig. 5 is angelica lactone polymkeric substance
1h-NMR collection of illustrative plates
Fig. 6 is angelica lactone polymkeric substance
1c-NMR collection of illustrative plates
Fig. 7 is the ESI-MS collection of illustrative plates of angelica lactone polymkeric substance
Embodiment
With specific embodiment, the present invention will be described below, but application of the present invention is not only confined to the scope listed by embodiment.
1, biomass by hydrolyzation prepares levulinic acid
Embodiment 1-8:
It is as follows that biomass by hydrolyzation prepares levulinic acid reaction equation:
(C
6h
10o
5)
n→ nC
5h
8o
3(levulinic acid)+nCH
2o
2
The aqueous hydrochloric acid being 5% by biomass starting material (wood chip, bagasse, sawdust, Mierocrystalline cellulose, stalk, absorbent cotton, fructose, glucose or starch) and mass concentration is put in autoclave according to the ratio that mass ratio is 1:10, be warming up to 140 DEG C, 200 DEG C or 220 DEG C, hydrolysis reaction 5,10 or 240min, cooled and filtered removing residue, obtains biomass hydrolysate.Product adopts waters UPLC to carry out qualitative and quantitative analysis.Biomass by hydrolyzation prepare levulinic acid reaction conditions and the results detailed in Table sequence number 1-8 in.
Table one embodiment 1-8 biomass by hydrolyzation prepares reaction conditions and the result of levulinic acid
| Embodiment | Reaction raw materials | Reaction times/min | Temperature of reaction/DEG C | Yield of levulinic acid/mol% |
| 1 | Mierocrystalline cellulose | 5 | 220 | 59.87 |
| 2 | Mierocrystalline cellulose | 10 | 200 | 55.07 |
| 3 | Mierocrystalline cellulose | 10 | 220 | 49.69 |
| 4 | Mierocrystalline cellulose | 240 | 140 | 50.25 |
| 5 | Stalk | 10 | 200 | 50.60 |
| 6 | Fructose | 10 | 200 | 56.94 |
| 7 | Glucose | 10 | 200 | 51.48 |
| 8 | Starch | 10 | 200 | 49.87 |
2, levulinic acid Dehydration is for angelica lactone
Embodiment 9-13:
Levulinic acid Dehydration is as follows for angelica lactone reaction equation:
C
5h
8o
3(levulinic acid) → C
5h
6o
2(angelica lactone)+H
2o
Flask put into by the levulinic acid taking 25g, adds the catalyzer H of its quality 3%
3pO
4or ZSM-5, be warming up to 130 DEG C, 160 DEG C, 175 DEG C or 180 DEG C under agitation, reaction 60min, 120min, 150min or 180min, control the vacuum tightness of reaction system, levulinic acid in reaction system gas phase is back to reaction system, angelica lactone steam distillates from still head, collects condensed fluid.Product adopts watersUPLC to carry out qualitative and quantitative analysis.Levulinic acid Dehydration is for the reaction conditions of angelica lactone and the results detailed in Table sequence number 9-13 in two.
Table two embodiment 9-13 levulinic acid Dehydration is for the reaction conditions of angelica lactone and result
| Embodiment | Catalyzer | Temperature of reaction/DEG C | Reaction times/min | Angelica lactone yield/mol% | Angelica lactone selectivity/% |
| 9 | H 3PO 4 | 130 | 180 | 54.71 | 69.98 |
| 10 | ZSM-5 | 130 | 180 | 91.65 | 91.65 |
| 11 | H 3PO 4 | 160 | 150 | 39.49 | 42.75 |
| 12 | H 3PO 4 | 175 | 120 | 57.52 | 97.26 |
| 13 | H 3PO 4 | 180 | 60 | 49.26 | 52.53 |
3, angelica lactone polymkeric substance is prepared in angelica lactone polymerization
Embodiment 14-21:
It is as follows that angelica lactone polymer reaction equation is prepared in angelica lactone polymerization:
NC
5h
6o
2(angelica lactone) → C
5nh
6no
2n(angelica lactone polymkeric substance)
The angelica lactone taking 30g puts into flask, is warming up to 60 DEG C, 80 DEG C, 100 DEG C, 120 DEG C, 140 DEG C or 160 DEG C, adds the catalyzer K of its quality 3% under agitation
2cO
3, reaction 1min, 5min, 30min, 120min or 180min, obtain Radix Angelicae Sinensis lactone polymer.Product adopts waters UPLC to carry out qualitative and quantitative analysis.Angelica lactone polymerization prepare angelica lactone polymkeric substance reaction conditions and the results detailed in Table sequence number 14-21 in three.
The reaction conditions of table three embodiment 14-21 angelica lactone polymerization and result
4, angelica lactone hydrogenation of polymer prepares biogasoline
Embodiment 22-28:
It is as follows that angelica lactone hydrogenation of polymer prepares biogasoline reaction equation:
C
5nh
6no
2n(angelica lactone polymkeric substance)+H
2→ C
nh
2n+2(biogasoline)+H
2o
The angelica lactone polymkeric substance taking 15g puts into autoclave, add catalyzer 10%Pd/C or NiFeCr of its quality 3%, hydrogen 5min is passed into replace the air in clean still in still, then pass into hydrogen to 5MPa, be warming up to 200 DEG C, 300 DEG C, 350 DEG C, 375 DEG C or 400 DEG C under agitation, reaction 4h, 12h, 18h or 60h, room temperature is cooled to after reaction terminates, slow releasing pressure is to normal atmosphere, and filtration residue, obtains biogasoline.Adopt GC-MS to carry out qualitative and quantitative analysis the biogasoline obtained, determined the kind of often kind of material by mass spectrum, adopt normalization method to carry out quantitatively.Obtain biological gasoline oil composition and content.The reaction conditions of angelica lactone hydrogenation of polymer and the results detailed in Table sequence number 22-28 in four.
The reaction conditions of table four embodiment 22-28 angelica lactone hydrogenation of polymer and result
What finally illustrate is, above embodiment is only in order to illustrate technical scheme of the present invention and unrestricted, although with reference to preferred embodiment to invention has been detailed description, those skilled in the art is to be understood that, can modify to technical scheme of the present invention or equivalent replacement, and not departing from the spirit and scope of technical solution of the present invention, it all should be encompassed in right of the present invention.
Claims (11)
1. one kind is the method that biogasoline prepared by raw material with biomass, it is characterized in that taking biomass as raw material, levulinic acid is prepared by biomass by hydrolyzation, levulinic acid Dehydration is for angelica lactone, angelica lactone polymkeric substance is prepared in angelica lactone polymerization, last angelica lactone hydrogenation of polymer deoxidation four step rule prepares biogasoline, its step is as follows: take mass concentration as 0.1%-10% hydrochloric acid or aqueous sulfuric acid be catalyzer, levulinic acid is prepared for raw material is hydrolyzed 5-240min at 140-220 DEG C of temperature with the biomass of acid solution quality 2%-10%, product levulinic acid is with the liquid acid of its quality 0.1-5%, acidic ion liquid or ZSM-5 molecular sieve are that catalyzer adopts integrated reaction and separation method reaction distillation 60-180min at 130-180 DEG C of temperature to prepare angelica lactone, angelica lactone is polymerized and prepares angelica lactone polymkeric substance to add Long carbon chain under mineral alkali catalysis, angelica lactone polymkeric substance hydrogenation deoxidation under catalyst action obtains product biogasoline.
2. a kind of is as claimed in claim 1 the method that biogasoline prepared by raw material with biomass, it is characterized in that: described biomass are wood chip, bagasse, sawdust, Mierocrystalline cellulose, stalk, absorbent cotton, fructose, glucose, starch.
3. a kind of is as claimed in claim 1 the method that biogasoline prepared by raw material with biomass, it is characterized in that: described angelica lactone liquid acid used of preparing is phosphoric acid, sulfuric acid, hydrochloric acid, and acidic ion liquid used is [DMIPA] [HSO
4], [(n-Bu-SO
3h) MIm] [HSO
4].
4. a kind of is as claimed in claim 1 the method that biogasoline prepared by raw material with biomass, it is characterized in that: described angelica lactone polymkeric substance inorganic base catalyst used of preparing is K
2cO
3, Na
2cO
3, NaHCO
3, Ca (OH)
2.
5. a kind of is as claimed in claim 1 the method that biogasoline prepared by raw material with biomass, it is characterized in that: the described catalyst levels prepared needed for angelica lactone polymkeric substance is the 0.1-5% of polymerizable raw material amount.
6. a kind of is as claimed in claim 1 the method that biogasoline prepared by raw material with biomass, it is characterized in that: the described angelica lactone polymkeric substance reaction times used of preparing is 1-180min.
7. a kind of is as claimed in claim 1 the method that biogasoline prepared by raw material with biomass, it is characterized in that: described angelica lactone polymkeric substance temperature of reaction used of preparing is 60-160 DEG C.
8. a kind of is as claimed in claim 1 the method that biogasoline prepared by raw material with biomass, it is characterized in that: it is 10%Pd/C, 5%Pd/C, NiFeCr, NiMoAl that described angelica lactone polymkeric substance prepares biogasoline catalyzer used.
9. a kind of is as claimed in claim 1 the method that biogasoline prepared by raw material with biomass, it is characterized in that: described angelica lactone polymkeric substance prepares the 0.1-5% that catalyst levels needed for biogasoline is polymerizable raw material amount.
10. a kind of is as claimed in claim 1 the method that biogasoline prepared by raw material with biomass, it is characterized in that: it is 4-60h that described angelica lactone hydrogenation of polymer prepares the biogasoline reaction times used.
11. a kind of be as claimed in claim 1 the method that biogasoline prepared by raw material with biomass, it is characterized in that: it is 200-400 DEG C that described angelica lactone hydrogenation of polymer prepares biogasoline temperature of reaction used.
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| CN104109563B true CN104109563B (en) | 2015-08-19 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102676201A (en) * | 2011-03-18 | 2012-09-19 | 赵晨 | Method for preparing high-quality gasoline from cracking biological oil |
| CN103524283A (en) * | 2013-10-12 | 2014-01-22 | 浙江大学 | Method for extracting monophenol compounds and pyrolysis lignin from biological oil |
-
2014
- 2014-07-23 CN CN201410352807.1A patent/CN104109563B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102676201A (en) * | 2011-03-18 | 2012-09-19 | 赵晨 | Method for preparing high-quality gasoline from cracking biological oil |
| CN103524283A (en) * | 2013-10-12 | 2014-01-22 | 浙江大学 | Method for extracting monophenol compounds and pyrolysis lignin from biological oil |
Non-Patent Citations (1)
| Title |
|---|
| 棉籽油加氢脱氧制备第二代生物柴油;董广达 等;《石油化工》;20130731;第42卷(第7期);737-742 * |
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