CN111234887A - Preparation method of long-chain oxygen-containing liquid fuel precursor - Google Patents
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- 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
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- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
Abstract
The invention discloses a preparation method of a long-chain oxygen-containing liquid fuel precursor, which comprises the following steps: adding 0.5-10 g of microcrystalline cellulose, 0.01-0.1 g of solid base catalyst and 30-50 g of hydrogen donor solvent into a reactor; replacing air in the reactor with inert gas, pressurizing to 2-4MPa at room temperature, and sealing the reactor; and step three, placing the reactor into a heating device, stirring at a stirring speed of 500-1000 r/min, heating to 260-340 ℃ at a speed of 5-150 ℃/min, reacting for 1-6 hours, quickly placing the reactor into ice water, cooling to room temperature, opening the reactor, and separating out a liquid-phase product to obtain the long-chain oxygen-containing liquid fuel precursor rich in the carbonyl compound. The invention utilizes cellulose to obtain a long-chain oxygen-containing fuel precursor rich in carbonyl compounds, and can directly prepare the long-chain oxygen-containing fuel through aldol condensation reaction, thereby improving the combustion and emission characteristics of the diesel engine.
Description
Technical Field
The invention relates to a preparation method of a fuel precursor, in particular to a preparation method of a long-chain oxygen-containing liquid fuel precursor.
Background
China has abundant biomass resources and large storage amount, but the effective utilization rate is less than 1%, and most of the biomass resources are buried or burned in the open air to cause energy waste and environmental pollution due to the lack of efficient conversion technology. On the other hand, in 2018, the imported petroleum in China is as high as 4.6 hundred million tons, the external dependence degree is increased to 70 percent, and the energy safety in China is seriously threatened. The biomass is used as the only renewable energy source containing carbon elements, the biomass-based liquid fuel can be directionally prepared by utilizing a fast pyrolysis or direct liquefaction technology to partially replace gasoline and diesel oil, the external dependence of petroleum in China can be relieved, the energy structure is optimized, and the clean and efficient utilization of biomass waste is realized.
At present, the process for preparing the oil from the biomass is carried out by the traditional petroleum refining route, and because the oxygen content in the biomass is higher than 30%, a noble metal catalyst and a large amount of hydrogen are required to be used for carrying out complete hydrodeoxygenation on the bio-oil, so that the whole process route is long, the production cost is high, and the process does not have the advantage of being competitive with fossil energy. On the other hand, the diesel engine belongs to a compression ignition combustion mode, and has a local oxygen deficiency condition, so that a large amount of soot emission is caused, and researches show that the emission of soot, NOx and HC can be effectively reduced by adding the oxygenated fuel into the diesel oil. The biomass-based oxygen-containing liquid fuels currently used for internal combustion engine research include alcohols (methanol, ethanol, etc.), ethers (dimethyl ether, acetal, etc.), esters (dimethyl carbonate, biodiesel, etc.), alcohol ethers (ethylene glycol dimethyl ether, diethylene glycol diethyl ether), and the like. Zjunqiang et al (science and technology of combustion, 2004,10(2), 171-: proper amount of methanol can improve the combustion characteristic of diesel engine and raise the heat efficiency of diesel engine, and with the increase of the methanol proportion in the mixed fuel, the CO and carbon smoke discharged from tail gas are reduced, but the NOx discharge is increased. Yang et al (Fuel, 2016,184, 681-. Liu et al [ Fuel,2016,177,206-216] studied the combustion and emission characteristics of diesel/polyoxymethylene dimethyl ether (PODE) mixed Fuel (PODE blending ratio of 15% to 25%) under different loads, and showed that PODE can promote the combustion rate in the later stage of combustion, and can effectively reduce the emission of conventional pollutants such as HC, CO and soot, and the original soot emission of PODE25 can reach the Euro VI soot emission standard. Therefore, the inherent oxygen atoms of the biomass are fully utilized, the oxygen-containing additive is prepared, the waste biomass resources can be efficiently utilized, the production cost is reduced, and the problem of environmental pollution caused by incomplete combustion of diesel oil can be avoided.
Generally, bio-oils are obtained mainly by two methods: fast pyrolysis and direct liquefaction. Compared with fast pyrolysis, the direct liquefaction technology has the advantages of wide raw material application, mild reaction conditions, high bio-oil quality, difficult carbon deposition and inactivation of the catalyst and the like, and is widely concerned. However, the liquefied bio-oil has complex oxygen-containing components, and the carbon chain lengths are all less than or equal to 6, which are not matched with the carbon chain length of diesel oil, so that the physical and chemical properties of the liquefied bio-oil and the diesel oil are greatly different, the liquefied bio-oil and the diesel oil cannot be mutually dissolved in any proportion, and the combustion activity is also poor.
Therefore, the carbon chain extending technology is needed to extend the carbon chain of the bio-based oxygen-containing fuel. Dumesic and Huber et al [ Science,2005,308,1446-]The method firstly researches that the sodium hydroxide catalyzes the cross aldol condensation reaction of biomass platform molecular acetone and 5-hydroxymethylfurfural/furfural to obtain the oxygen-containing organic compound within the chain length range of the aviation kerosene, the conversion rate can reach 100 percent, but the whole process needs the n-hexadecane to dissolve the condensation product and prevent the catalyst from being inactivated. Liang et al [ Greenchemistry,2016,18,3430-]Study of a series of alkali metal oxides (MgO, ZnO, TiO, ZrO)2，MgO-Al2O3，CeO2，Nb2O5，SnO2，WO3) The cross aldol condensation reaction between the levulinic acid and the furfural is catalyzed by the acidic zeolite (HY, H β -5, H-MOR, SAPO-34), the result shows that ZnO has the highest activity, the yield of the C11 oxygen-containing compound reaches 80.9 percent, and the product needs to be separated and purified because the whole reaction takes water as a solvent, thereby increasing the operation cost.
The current process for preparing the biomass-based oxygen-containing liquid fuel mainly has the following problems: the biomass does not separate lignin, the existence of lignin which is difficult to depolymerize prevents the polysaccharide component from fully contacting with a catalyst in the conversion process, so that the components of the liquefied product are complex, the carbon chain is short, the yield is low, the obtained product contains a large amount of ethers, phenols and acid compounds, and the carbon chain growth is difficult to carry out without separation and purification.
Disclosure of Invention
The purpose of the invention is as follows: in order to overcome the defects in the prior art, the invention aims to provide the preparation method of the long-chain oxygen-containing liquid fuel precursor, which has the advantages of simple process, low energy consumption, high yield and high selectivity.
The technical scheme is as follows: the preparation method of the long-chain oxygen-containing liquid fuel precursor comprises the following steps:
adding 0.5-10 g of microcrystalline cellulose, 0.01-0.1 g of solid base catalyst and 30-50 g of hydrogen donor solvent into a reactor;
replacing air in the reactor with inert gas, pressurizing to 2-4MPa at room temperature, and sealing the reactor;
and step three, placing the reactor into a heating device, stirring at a stirring speed of 500-1000 r/min, heating to 260-340 ℃ at a speed of 5-150 ℃/min, reacting for 1-6 hours, quickly placing the reactor into ice water, cooling to room temperature, opening the reactor, and separating out a liquid-phase product to obtain the long-chain oxygen-containing liquid fuel precursor rich in the carbonyl compound.
Wherein the solid base catalyst is CaO, MgO, La2O3And one or more of ZnO have strong ability of abstracting proton, so that the alcoholysis reaction of the cellulose on the surface of the catalyst can be promoted to generate more small molecular ester compounds. Compared with an acid catalyst, the solid base catalyst does not corrode reaction equipment, and can simultaneously convert all levorotatory glucose and alkyl glucoside into small molecular products under certain conditions, so that the yield of carbonyl compounds in a liquid-phase product is improved. The hydrogen donor solvent is one of methanol, ethanol, isopropanol, water and methanol mixture, water and ethanol mixture, and water and isopropanol mixtureThe long-chain oxygen-containing liquid fuel is a carbonyl compound with α -H, and the carbonyl compound with α -H is a mixture of ketones, esters, furfurals and aldehydes.
Has the advantages that: compared with the prior art, the invention has the following remarkable characteristics:
1. cellulose is utilized to obtain a long-chain oxygen-containing fuel precursor rich in carbonyl compounds, and the long-chain oxygen-containing fuel can be directly prepared through aldol condensation reaction, so that the combustion and emission characteristics of a diesel engine are improved;
2. the hydrogen donor solvent has lower critical temperature and critical pressure, and the depolymerized product can directly carry out carbon chain growth reaction without separation, thereby reducing the production cost.
Drawings
FIG. 1 is a chromatogram of the liquefaction product of cellulose in different catalyst systems;
FIG. 2 shows the yields of carbonyl compounds in the product of cellulose liquefaction under different conditions.
Detailed Description
The raw materials used in the following examples were all purchased directly. The reactors were all batch type high temperature high pressure reactors (MC-50, Beijing century Senlang laboratory instruments Co., Ltd.).
Example 1
A preparation method of a long-chain oxygen-containing liquid fuel precursor comprises the following steps:
step one, adding 0.5g of microcrystalline cellulose, 0.01g of solid base catalyst CaO and 30g of hydrogen donor solvent methanol into a reactor;
replacing air in the reactor with inert gas nitrogen, pressurizing to 2MPa at room temperature, and sealing the reactor;
and step three, placing the reactor into a heating device, stirring at a stirring speed of 500r/min, heating to 260 ℃ at a speed of 5 ℃/min, reacting for 1 hour, quickly placing the reactor into ice water, cooling to room temperature, opening the reactor, and separating a liquid-phase product to obtain a long-chain oxygen-containing liquid fuel precursor rich in carbonyl compounds, namely the carbonyl compounds with α -H, including ketone, ester, furfuraldehyde and aldehyde mixtures.
Example 2
A preparation method of a long-chain oxygen-containing liquid fuel precursor comprises the following steps:
step one, adding 10g of microcrystalline cellulose, 0.1g of solid base catalyst MgO and 50g of hydrogen donor solvent ethanol into a reactor;
replacing air in the reactor with helium which is an inert gas, pressurizing to 4MPa at room temperature, and sealing the reactor;
and step three, placing the reactor into a heating device, stirring at a stirring speed of 1000r/min, heating to 340 ℃ at a speed of 150 ℃/min, reacting for 6 hours, quickly placing the reactor into ice water, cooling to room temperature, opening the reactor, and separating a liquid-phase product to obtain a long-chain oxygen-containing liquid fuel precursor rich in carbonyl compounds, namely the carbonyl compounds with α -H, including ketone, ester, furfuraldehyde and aldehyde mixtures.
Example 3
A preparation method of a long-chain oxygen-containing liquid fuel precursor comprises the following steps:
step one, adding 5.5g of microcrystalline cellulose and 0.05g of solid alkali catalyst La into a reactor2O3And 40g of isopropanol as hydrogen donor solvent;
replacing air in the reactor with inert gas argon, pressurizing to 3MPa at room temperature, and sealing the reactor;
and step three, placing the reactor into a heating device, stirring at a stirring speed of 750r/min, heating to 300 ℃ at a speed of 76 ℃/min, reacting for 3.5 hours, quickly placing the reactor into ice water, cooling to room temperature, opening the reactor, and separating an aqueous product to obtain a long-chain oxygen-containing liquid fuel precursor rich in the carbonyl compound, namely the carbonyl compound with α -H, including a mixture of ketones, esters, furfurals and aldehydes.
Example 4
A preparation method of a long-chain oxygen-containing liquid fuel precursor comprises the following steps:
adding a mixture of 1g of microcrystalline cellulose, 0.02g of ZnO as a solid base catalyst and 35g of water, methanol and ethanol as hydrogen donor solvents into a reactor;
replacing air in the reactor with inert gases of nitrogen and helium, pressurizing to 2.5MPa at room temperature, and sealing the reactor;
and step three, placing the reactor into a heating device, stirring at a stirring speed of 600r/min, heating to 270 ℃ at a speed of 10 ℃/min, reacting for 2 hours, quickly placing the reactor into ice water, cooling to room temperature, opening the reactor, and separating a liquid-phase product to obtain a long-chain oxygen-containing liquid fuel precursor rich in carbonyl compounds, namely the carbonyl compounds with α -H, including ketone, ester, furfuraldehyde and aldehyde mixtures.
Example 5
A preparation method of a long-chain oxygen-containing liquid fuel precursor comprises the following steps:
adding 9g of microcrystalline cellulose, 0.09g of a solid base catalyst CaO and ZnO mixture, and 45g of a hydrogen donor solvent ethanol, isopropanol and water mixture into a reactor;
replacing air in the reactor with inert gases such as nitrogen and argon, pressurizing to 3.5MPa at room temperature, and sealing the reactor;
and step three, placing the reactor into a heating device, stirring at a stirring speed of 900r/min, heating to 320 ℃ at a speed of 140 ℃/min, reacting for 5 hours, quickly placing the reactor into ice water, cooling to room temperature, opening the reactor, and separating a liquid-phase product to obtain a long-chain oxygen-containing liquid fuel precursor rich in carbonyl compounds, namely the carbonyl compounds with α -H, including ketone, ester, furfuraldehyde and aldehyde mixtures.
Example 6
A preparation method of a long-chain oxygen-containing liquid fuel precursor comprises the following steps:
step one, 1.5g of microcrystalline cellulose and 0.04g of solid alkali catalyst La are added into a reactor2O3And 39g of ethanol as a hydrogen donor solvent;
replacing air in the reactor with inert gas nitrogen, pressurizing to 3MPa at room temperature, and sealing the reactor;
and step three, placing the reactor into a heating device, stirring at a stirring speed of 700r/min, heating to 280 ℃ at a speed of 20 ℃/min, reacting for 3 hours, quickly placing the reactor into ice water, cooling to room temperature, opening the reactor, and separating a liquid-phase product to obtain a long-chain oxygen-containing liquid fuel precursor rich in carbonyl compounds, namely the carbonyl compounds with α -H, including ketone, ester, furfuraldehyde and aldehyde mixtures.
Example 7
A preparation method of a long-chain oxygen-containing liquid fuel precursor comprises the following steps:
step one, 1.5g of microcrystalline cellulose and 0.04g of solid alkali catalyst La are added into a reactor2O3And 39g of a hydrogen donating solvent, i.e. a mixture of ethanol and water, wherein 9g of water, 30g of ethanol;
replacing air in the reactor with inert gas nitrogen, pressurizing to 3MPa at room temperature, and sealing the reactor;
and step three, placing the reactor into a heating device, stirring at a stirring speed of 700r/min, heating to 280 ℃ at a speed of 20 ℃/min, reacting for 3 hours, quickly placing the reactor into ice water, cooling to room temperature, opening the reactor, and separating a liquid-phase product to obtain a long-chain oxygen-containing liquid fuel precursor rich in carbonyl compounds, namely the carbonyl compounds with α -H, including ketone, ester, furfuraldehyde and aldehyde mixtures.
The products of example 6 and example 7 were subjected to GC-MS testing as shown in fig. 1, where it can be seen that La is compared to ethanol as solvent2O3Catalyzing cellulose to depolymerize in a water-ethanol mixed solvent to obtain more carbonyl compounds,such as ethyl lactate and ethyl levulinate, because supercritical water has acidic and basic properties that promote hydrolysis, isomerization, esterification, and the like.
Example 8
A preparation method of a long-chain oxygen-containing liquid fuel precursor comprises the following steps:
step one, adding 7g of microcrystalline cellulose and 33g of hydrogen donor solvent ethanol into a reactor;
replacing air in the reactor with helium which is an inert gas, pressurizing to 4MPa at room temperature, and sealing the reactor;
and step three, placing the reactor into a heating device, stirring at a stirring speed of 900r/min, heating to 320 ℃ at a speed of 130 ℃/min, reacting for 5 hours, quickly placing the reactor into ice water, cooling to room temperature, opening the reactor, and separating a liquid-phase product to obtain a long-chain oxygen-containing liquid fuel precursor rich in carbonyl compounds, namely the carbonyl compounds with α -H, including ketone, ester, furfuraldehyde and aldehyde mixtures.
Example 9
A preparation method of a long-chain oxygen-containing liquid fuel precursor comprises the following steps:
step one, adding 7g of microcrystalline cellulose, 0.03g of ZnO as a solid base catalyst and 33g of ethanol as a hydrogen supply solvent into a reactor;
replacing air in the reactor with helium which is an inert gas, pressurizing to 4MPa at room temperature, and sealing the reactor;
and step three, placing the reactor into a heating device, stirring at a stirring speed of 900r/min, heating to 320 ℃ at a speed of 130 ℃/min, reacting for 5 hours, quickly placing the reactor into ice water, cooling to room temperature, opening the reactor, and separating a liquid-phase product to obtain a long-chain oxygen-containing liquid fuel precursor rich in carbonyl compounds, namely the carbonyl compounds with α -H, including ketone, ester, furfuraldehyde and aldehyde mixtures.
Example 10
A preparation method of a long-chain oxygen-containing liquid fuel precursor comprises the following steps:
adding 7g of microcrystalline cellulose, 0.03g of solid base catalyst ZnO and 33g of hydrogen donor solvent into a reactor, wherein the weight of water is 9g, and the weight of ethanol is 30 g;
replacing air in the reactor with helium which is an inert gas, pressurizing to 4MPa at room temperature, and sealing the reactor;
and step three, placing the reactor into a heating device, stirring at a stirring speed of 900r/min, heating to 320 ℃ at a speed of 130 ℃/min, reacting for 5 hours, quickly placing the reactor into ice water, cooling to room temperature, opening the reactor, and separating a liquid-phase product to obtain a long-chain oxygen-containing liquid fuel precursor rich in carbonyl compounds, namely the carbonyl compounds with α -H, including ketone, ester, furfuraldehyde and aldehyde mixtures.
The yields of the products in examples 8 to 10 are respectively calculated, as shown in fig. 2, it can be seen that the yield of the carbonyl compound in the product of alcoholysis liquefaction of cellulose catalyzed by ZnO is increased from 9.61% to 47.52%, the yield of the carbonyl compound in the water-ethanol composite solvent is significantly increased to 89.41%, and the solvent and the liquid phase product can be directly subjected to the next aldol condensation reaction without separation to prepare the long-chain oxygen-containing liquid fuel.
Example 11
A preparation method of a long-chain oxygen-containing liquid fuel precursor comprises the following steps:
step one, adding 1g of microcrystalline cellulose, 0.01g of solid base catalyst MgO and 30g of hydrogen donor solvent ethanol into a reactor;
replacing air in the reactor with inert gas nitrogen, pressurizing to 2MPa at room temperature, and sealing the reactor;
and step three, placing the reactor into a heating device, stirring at a stirring speed of 500r/min, heating to 320 ℃ at a speed of 10 ℃/min, reacting for 1 hour, quickly placing the reactor into ice water, cooling to room temperature, opening the reactor, and separating a liquid-phase product to obtain a long-chain oxygen-containing liquid fuel precursor rich in carbonyl compounds, namely the carbonyl compounds with α -H, including ketone, ester, furfuraldehyde and aldehyde mixtures.
Example 12
A preparation method of a long-chain oxygen-containing liquid fuel precursor comprises the following steps:
step one, adding 1g of microcrystalline cellulose, 0.01g of solid base catalyst CaO and 30g of hydrogen donor solvent ethanol into a reactor;
replacing air in the reactor with inert gas nitrogen, pressurizing to 2MPa at room temperature, and sealing the reactor;
and step three, placing the reactor into a heating device, stirring at a stirring speed of 500r/min, heating to 320 ℃ at a speed of 10 ℃/min, reacting for 1 hour, quickly placing the reactor into ice water, cooling to room temperature, opening the reactor, and separating a liquid-phase product to obtain a long-chain oxygen-containing liquid fuel precursor rich in carbonyl compounds, namely the carbonyl compounds with α -H, including ketone, ester, furfuraldehyde and aldehyde mixtures.
Example 13
A preparation method of a long-chain oxygen-containing liquid fuel precursor comprises the following steps:
step one, adding 1g of microcrystalline cellulose, 0.01g of ZnO as a solid base catalyst and 30g of ethanol as a hydrogen donor solvent into a reactor;
replacing air in the reactor with inert gas nitrogen, pressurizing to 2MPa at room temperature, and sealing the reactor;
and step three, placing the reactor into a heating device, stirring at a stirring speed of 500r/min, heating to 320 ℃ at a speed of 10 ℃/min, reacting for 1 hour, quickly placing the reactor into ice water, cooling to room temperature, opening the reactor, and separating a liquid-phase product to obtain a long-chain oxygen-containing liquid fuel precursor rich in carbonyl compounds, namely the carbonyl compounds with α -H, including ketone, ester, furfuraldehyde and aldehyde mixtures.
Example 14
A preparation method of a long-chain oxygen-containing liquid fuel precursor comprises the following steps:
step one, adding 1g of microcrystalline cellulose, 0.01g of solid base catalyst ZnO, 30g of hydrogen donor solvent and a mixture of water and ethanol into a reactor, wherein the mass ratio of the water to the ethanol is 1: 10;
replacing air in the reactor with inert gas nitrogen, pressurizing to 2MPa at room temperature, and sealing the reactor;
and step three, placing the reactor into a heating device, stirring at a stirring speed of 500r/min, heating to 320 ℃ at a speed of 10 ℃/min, reacting for 1 hour, quickly placing the reactor into ice water, cooling to room temperature, opening the reactor, and separating a liquid-phase product to obtain a long-chain oxygen-containing liquid fuel precursor rich in carbonyl compounds, namely the carbonyl compounds with α -H, including ketone, ester, furfuraldehyde and aldehyde mixtures.
Example 15
A preparation method of a long-chain oxygen-containing liquid fuel precursor comprises the following steps:
step one, adding 1g of microcrystalline cellulose, 0.01g of solid base catalyst ZnO, 30g of hydrogen donor solvent and a mixture of water and ethanol into a reactor, wherein the mass ratio of the water to the ethanol is 3: 10;
replacing air in the reactor with inert gas nitrogen, pressurizing to 2MPa at room temperature, and sealing the reactor;
and step three, placing the reactor into a heating device, stirring at a stirring speed of 500r/min, heating to 320 ℃ at a speed of 10 ℃/min, reacting for 1 hour, quickly placing the reactor into ice water, cooling to room temperature, opening the reactor, and separating a liquid-phase product to obtain a long-chain oxygen-containing liquid fuel precursor rich in carbonyl compounds, namely the carbonyl compounds with α -H, including ketone, ester, furfuraldehyde and aldehyde mixtures.
Example 16
A preparation method of a long-chain oxygen-containing liquid fuel precursor comprises the following steps:
step one, adding 1g of microcrystalline cellulose, 0.01g of solid base catalyst ZnO, 30g of hydrogen donor solvent and a mixture of water and ethanol into a reactor, wherein the mass ratio of the water to the ethanol is 3: 5;
replacing air in the reactor with inert gas nitrogen, pressurizing to 2MPa at room temperature, and sealing the reactor;
and step three, placing the reactor into a heating device, stirring at a stirring speed of 500r/min, heating to 320 ℃ at a speed of 10 ℃/min, reacting for 1 hour, quickly placing the reactor into ice water, cooling to room temperature, opening the reactor, and separating a liquid-phase product to obtain a long-chain oxygen-containing liquid fuel precursor rich in carbonyl compounds, namely the carbonyl compounds with α -H, including ketone, ester, furfuraldehyde and aldehyde mixtures.
TABLE 1 alkali metal oxide catalyzed depolymerization of cellulose in hydrogen donating solvents
| Examples | Reaction temperature/. degree.C | Catalyst and process for preparing same | Hydrogen donor solvent | Yield/wt.% of target product |
| Example 11 | 320 | MgO | Ethanol | 41.07 |
| Example 12 | 320 | CaO | Ethanol | 36.21 |
| Example 13 | 320 | ZnO | Ethanol | 47.52 |
| Example 14 | 320 | ZnO | Water: ethanol ═ 1: 10 | 76.80 |
| Example 15 | 320 | ZnO | Water: ethanol ═ 3: 10 | 89.41 |
| Example 16 | 320 | ZnO | Water: ethanol ═ 3: 5 | 56.39 |
The yields of the target products in examples 11-16 are summarized in Table 1, and it can be seen that: the ZnO catalyzed cellulose has the best effect of liquefying in a water-ethanol mixed solvent (the mass ratio of water to ethanol is 3: 10), the yield of a target product can reach 89.41%, and the ZnO catalyzed cellulose can be directly used as a substrate of aldol condensation reaction to carry out carbon chain growth, so that the long-chain oxygen-containing liquid fuel is prepared.
Claims (10)
1. A preparation method of a long-chain oxygen-containing liquid fuel precursor is characterized by comprising the following steps:
step one, adding microcrystalline cellulose, a solid base catalyst and a hydrogen donor solvent into a reactor;
replacing air in the reactor with inert gas, pressurizing to 2-4MPa at room temperature, and sealing the reactor;
and step three, placing the reactor into a heating device, stirring and heating, after the reaction is finished, rapidly placing the reactor into ice water, cooling to room temperature, opening the reactor, and separating a liquid-phase product to obtain the long-chain oxygen-containing liquid fuel precursor rich in the carbonyl compound.
2. The method for preparing the long-chain oxygen-containing liquid fuel precursor as claimed in claim 1, wherein the method comprises the following steps: the solid base catalyst is CaO, MgO, La2O3And ZnO.
3. The method for preparing the long-chain oxygen-containing liquid fuel precursor as claimed in claim 1, wherein the method comprises the following steps: the hydrogen donor solvent is one or more of methanol, ethanol, isopropanol, a mixture of water and methanol, a mixture of water and ethanol, and a mixture of water and isopropanol.
4. The method for preparing the long-chain oxygen-containing liquid fuel precursor as claimed in claim 1, wherein the method comprises the following steps: the inert gas is one or more of nitrogen, helium and argon.
5. The method for preparing the long-chain oxygen-containing liquid fuel precursor as claimed in claim 1, wherein the method comprises the following steps: the addition amount of the microcrystalline cellulose is 0.5-10 g, the addition amount of the solid alkali catalyst is 0.01-0.1 g, and the addition amount of the hydrogen donor solvent is 30-50 g.
6. The method for preparing the long-chain oxygen-containing liquid fuel precursor as claimed in claim 1, wherein the method comprises the following steps: in the third step, the temperature is increased to 260-340 ℃ at the speed of 5-150 ℃/min, and the reaction time is 1-6 hours.
7. The method for preparing the long-chain oxygen-containing liquid fuel precursor as claimed in claim 1, wherein the method comprises the following steps: in the third step, the stirring speed is 500-1000 r/min.
8. The method for preparing the long-chain oxygen-containing liquid fuel precursor as claimed in claim 1, wherein the method comprises the following steps: the reactor is an intermittent high-temperature high-pressure reaction kettle.
9. The preparation method of the long-chain oxygen-containing liquid fuel precursor is characterized in that the long-chain oxygen-containing liquid fuel precursor is a carbonyl compound with α -H.
10. The method for preparing the long-chain oxygen-containing liquid fuel precursor as claimed in claim 9, wherein the carbonyl compound having α -H is a ketone, an ester, a furfuraldehyde, or an aldehyde mixture.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103897717A (en) * | 2012-12-25 | 2014-07-02 | 中国科学院大连化学物理研究所 | Method used for preparing liquid fuel from cellulose |
| CN103897716A (en) * | 2012-12-25 | 2014-07-02 | 中国科学院大连化学物理研究所 | Method used for preparing liquid fuel from glucose |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103897717A (en) * | 2012-12-25 | 2014-07-02 | 中国科学院大连化学物理研究所 | Method used for preparing liquid fuel from cellulose |
| CN103897716A (en) * | 2012-12-25 | 2014-07-02 | 中国科学院大连化学物理研究所 | Method used for preparing liquid fuel from glucose |
Non-Patent Citations (2)
| Title |
|---|
| 贺小亮等: ""微晶纤维素复合溶剂醇解制备乙酰丙酸甲酯的研究"", 《现代化工》 * |
| 邹群等: ""金属氧化物催化热解微晶纤维素"", 《化工进展》 * |
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