CN114874802A - Method for improving yield of carbohydrate biomass hydrothermal liquefaction bio-oil - Google Patents
Method for improving yield of carbohydrate biomass hydrothermal liquefaction bio-oil Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 35
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- 239000012429 reaction media Substances 0.000 claims abstract description 28
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- 230000007613 environmental effect Effects 0.000 description 2
- 210000003608 fece Anatomy 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
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- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
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- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 1
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- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 229940027991 antiseptic and disinfectant quinoline derivative Drugs 0.000 description 1
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 1
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- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000010806 kitchen waste Substances 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 239000010871 livestock manure Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
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- 238000002360 preparation method Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 125000002943 quinolinyl group Chemical class N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/008—Controlling or regulating of liquefaction processes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1011—Biomass
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4006—Temperature
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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- Chemical & Material Sciences (AREA)
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- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention belongs to the technical field of new energy, and particularly relates to a method for improving the yield of carbohydrate biomass hydrothermal liquefied bio-oil, wherein the obtained bio-oil can be further upgraded to prepare traffic fuels or products with high added values. The invention provides a method for hydro-thermally liquefying bio-oil by carbohydrate biomass, which comprises the following steps: carrying out hydrothermal liquefaction on carbohydrate biomass in a reaction medium; the reaction medium is an aqueous phase product obtained after the protein biomass is hydrothermally liquefied, the aqueous phase product refers to water obtained after the protein biomass is hydrothermally liquefied and various compounds dissolved in the water, nitrogen-containing compounds such as amino acids in the aqueous phase product obtained after the protein biomass is hydrothermally liquefied react with components such as reducing sugar generated in the process of the hydrothermal liquefaction of carbohydrates, the bio-oil yield of the carbohydrate biomass can be remarkably improved, organic components in the aqueous phase obtained after the high-protein biomass is hydrothermally liquefied can be fully utilized, and the resource utilization of the aqueous phase product is realized.
Description
Technical Field
The invention belongs to the technical field of new energy, and particularly relates to a method for improving the yield of carbohydrate biomass hydrothermal liquefied bio-oil, wherein the obtained bio-oil can be further upgraded to prepare traffic fuels or products with high added values.
Background
The biomass energy is the energy which is second to coal, petroleum and natural gas and is the fourth of the total energy consumption of the world, and plays an important role in the whole energy system. The biomass is renewable, rich in total amount and carbon neutral, so that the biomass is favored by people. Among many biomasses, the yields of agricultural and forestry biomasses such as straws are huge, and the thermochemical conversion technology is a common way to convert biomasses such as straws into liquid fuels.
Hydrothermal liquefaction (hydro thermo liquefaction) is one of the biomass thermochemical conversion technologies. The method is characterized in that water is used as a solvent, biomass is converted into liquid organic micromolecules through depolymerization, bond breaking, decarboxylation and other actions at a certain temperature (200-370 ℃) and under a pressure (5-22MPa), then the unstable micromolecules are polymerized again to generate a liquid product, and the separated liquid fuel is called as bio-oil.
Compared with other liquid fuel production technologies (oil extraction or cracking and the like), the hydrothermal liquefaction technology has the remarkable characteristics that: (1) the oil formation mechanism is different. The hydrothermal liquefaction can utilize not only fat but also carbohydrates, proteins and the like in the biomass, and can realize the complete conversion of the biomass. (2) The raw materials have wide sources. Algae, straws, livestock and poultry manure, food waste, kitchen waste and the like can be subjected to hydrothermal conversion. (3) The water content of the raw material is high. Different from the cracking technology, the hydrothermal liquefaction can use biomass with the water content of more than 70% as a raw material, and the raw material does not need to be dried and pretreated. Therefore, the hydrothermal liquefaction conversion technology can be used as one of the ways for the efficient utilization of biomass resources.
But the oil yield of carbohydrate biomass is relatively low. For example, pure cellulose is used as raw material, and the bio-oil yield is generally lower than 10% (Lu J, Liu Z, Zhang Y, Savage PE. synergistic and anti-inflammatory interactions along with hydro-thermal lipid of soy oil, soy protein, cellulose, xylose, and lignin. ACS sustatin. chem. Eng.2018,6(11):14501 and 14509); straw is used as a raw material, and the bio-oil yield of the straw is generally 14-26% (Liu, H., Feng, B., Sun, R.,2011. Acid-chloride Pretreatment and lipid analysis of corn in hot-complex water for bio-oil production. J. age. food. chem.59, 10524-10531; patent CN 103265967B; CN 105733641A). There is therefore a need to find ways to increase the yield of carbohydrate biomass bio-oil.
The prior art proposes various ways for improving the yield of the carbohydrate biomass bio-oil, mainly including adding a catalyst, a hydrogen donor solvent, and liquefying with other biomass in a synergistic way, but the ways also bring new problems, such as difficult recovery of the catalyst, high cost, and the like.
Patent CN107029727B discloses a preparation method of nickel and titanium dioxide powder catalyst, which is beneficial to improving the yield and quality of bio-oil, but because the hydrothermal liquefaction product contains solids, the catalyst is difficult to recover, and the oil production cost is increased.
The patent CN103265967B introduces a hydrogen donor solvent into a biomass hydrothermal liquefaction system, obtains higher bio-oil yield, but consumes a large amount of organic solvent, so that the oil production cost is greatly increased.
The literature (Yang J, Sophia He Q, Yang L.A review on hydrotherma co-liquidation of biomass. Appl. energy.2019, 250: 926-. After the biomass is hydrothermally liquefied, besides the main product bio-oil, a plurality of aqueous phase products also contain a plurality of organic components, and the influence of the hydrothermal liquefied aqueous phase on the bio-oil yield is researched by repeatedly using the hydrothermal liquefied aqueous phase as a reaction medium, such as the literature (Zhu Z, Rosendahl L, Toor SS, Yu D, Chen G. hydrothermal Liquefaction of stalk strain to bio-oil: Effects of reaction temperature and aqueous phase registration. application. energy. 2015,137: 183. 192) continues the barley straw liquefaction reaction by using the aqueous phase product after the barley straw is hydrothermally liquefied as the reaction medium, but the repeated use of the aqueous phase is found to have no obvious influence on the bio-oil yield and hardly change in the bio-oil yield, which is probably because the organic matter in the aqueous phase is generated in the barley straw hydrothermal liquefaction process and is difficult to continue the reaction with the barley straw, the contribution to the bio-oil yield is small.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for improving the yield of the carbohydrate biomass hydrothermal liquefaction bio-oil. The method not only obviously improves the bio-oil yield of carbohydrate, but also enables the water-phase product of the high-protein biomass after hydrothermal liquefaction to be recycled, and greatly improves the comprehensive economic benefit; meanwhile, the method does not need additional water, saves water resources and is beneficial to environmental protection.
The invention provides a method for hydro-thermally liquefying bio-oil by carbohydrate biomass, which comprises the following steps: performing hydrothermal liquefaction on carbohydrate biomass in a reaction medium at a certain temperature; the reaction medium is a water-phase product obtained after protein biomass is hydrothermally liquefied.
The method selects the aqueous phase product of the protein biomass after hydrothermal liquefaction as a reaction medium, and utilizes nitrogen-containing compounds such as amino acid and the like in the aqueous phase product of the protein biomass after hydrothermal liquefaction to react with components such as reducing sugar and the like generated in the hydrothermal liquefaction process of the carbohydrate, so that the yield of the biological oil of the carbohydrate biomass can be obviously improved, and meanwhile, organic components in the aqueous phase of the high-protein biomass after hydrothermal liquefaction can be fully utilized, and the recycling of the aqueous phase product is realized.
Further, the water phase product after the protein biomass is hydrothermally liquefied mainly contains the following components except water: nitrogen-containing compounds, phenols, ketones, and the like; wherein, the content of the nitrogen-containing compounds such as ammonia, chain amide, amino acid, pyridine, indole and the like accounts for 60-80%, the content of the phenolic compounds accounts for 1-8% and the content of the ketone compounds accounts for 3-15% of the water phase products except water. Compared with other aqueous phase products containing nitrogen compounds after the biomass is hydrothermally liquefied, the aqueous phase product after the protein biomass is hydrothermally liquefied has high content of the nitrogen compounds (ammonia, amino acid and derivatives thereof), is easy to perform chemical reaction (Maillard reaction and the like) with glucose generated in the lignocellulose hydrothermal process to generate a plurality of bio-oil components (pyrrolidone, quinoline derivatives and the like), and can remarkably improve the bio-oil yield by selecting the bio-oil components as reaction media for the hydrothermal liquefaction of carbohydrate biomass.
In the present invention, the protein content of the proteinaceous biomass is at least 50% or more; preferably, the protein biomass is selected from high protein biomass such as soy protein, chlorella, spirulina and the like.
The mass ratio of the carbohydrate biomass to the protein biomass hydrothermal liquefaction water-phase product is 1: 100-1: 3; the specific method can be determined according to the types of the carbohydrate biomass and the components of the aqueous phase product of the hydrothermal liquefaction of the protein biomass.
Further, the reaction conditions of the hydrothermal liquefaction are as follows: the temperature is 260-360 ℃, and the time is 1-300 min. The specific temperature and time can be adjusted according to the type of carbohydrate biomass and the composition of the aqueous phase product of the hydrothermal liquefaction of the protein biomass. The hydrothermal liquefaction reaction trans-form of the invention can be a batch type or a continuous type.
Further, after the hydrothermal liquefaction reaction is finished, cooling the obtained mixed solution, collecting gas, filtering to obtain a water phase, performing ultrasonic extraction, performing reduced pressure filtration, distilling, and drying to obtain the bio-oil. Wherein the extractant used in the extraction is one of acetone, dichloromethane and ethyl acetate.
The carbohydrate biomass provided by the invention is cellulose, straw, pine, sawdust and the like.
In addition, the invention also finds that the carbohydrate biomass has a specific matching relation with a reaction medium and reaction conditions, and if the elements are not matched, the bio-oil yield is correspondingly reduced. To this end, as a specific embodiment of the present invention, the carbohydrate biomass is cellulose, and the reaction medium is a soy protein hydrothermal liquefaction aqueous phase product; the mass ratio of the carbohydrate biomass to the reaction medium is 1: (9-10), conditions of hydrothermal liquefaction: the temperature is 280-285 ℃, and the time is 25-30 min;
or the carbohydrate biomass is straw, and the reaction medium is a soybean protein hydrothermal liquefaction water-phase product; the mass ratio of the carbohydrate biomass to the reaction medium is 1: (40-42), conditions of hydrothermal liquefaction: the temperature is 360-365 ℃, and the time is 8-10 min;
or the carbohydrate biomass is pine wood, and the reaction medium is a chlorella hydrothermal liquefaction water-phase product; the mass ratio of the carbohydrate biomass to the reaction medium is 1: (3-3.5), conditions of hydrothermal liquefaction: the temperature is 260-265 ℃, and the time is 290-300 min;
or the carbohydrate biomass is sawdust, and the reaction medium is a spirulina hydrothermal liquefaction water-phase product; the mass ratio of the carbohydrate biomass to the reaction medium is 1: (10-11), conditions of hydrothermal liquefaction: the temperature is 320 ℃ and 330 ℃, and the time is 90-100 min.
The invention has the following beneficial effects:
1. according to the invention, the carbohydrate biomass is hydrothermally liquefied in the water-phase product of the high-protein biomass after hydrothermal liquefaction, so that the carbohydrate biomass is utilized, the water-phase product of the high-protein biomass after hydrothermal liquefaction is recycled, and the bio-oil yield of the carbohydrate is obviously improved.
2. The utilization of the high-protein biomass water-phase product can also ensure that additional water is not needed in the hydrothermal liquefaction process, thereby saving water resources and being beneficial to environmental protection.
Drawings
FIG. 1 is a process flow diagram of the method of the present invention.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example 1
The embodiment provides a method for hydro-thermally liquefying bio-oil by carbohydrate biomass, which comprises the following steps:
(1) adding 1g of straw biomass and 40g of soybean protein hydrothermal liquefaction water-phase product into a reaction kettle and sealing.
(2) Heating the reaction kettle to 360 ℃, keeping the temperature for 10min, then stopping heating, and cooling the reaction kettle to room temperature.
(3) After the reaction kettle is cooled to room temperature, the gas is collected firstly, then the reaction kettle is opened, the product is collected by a glass cup, and a water phase is obtained by a reduced pressure filtration mode.
The kettle body and the residual solid product are washed by dichloromethane, and the dichloromethane and the solid product mixture is placed into a beaker and subjected to ultrasonic waves for 30 min.
(4) And filtering the product after ultrasonic extraction under reduced pressure to obtain a solid residue, wherein the liquid phase part after filtration is a mixed phase of dichloromethane and bio-oil, pouring the mixed phase into an extraction bottle, and distilling to recover dichloromethane.
(5) Putting the product obtained after the dichloromethane is removed into a drying oven for drying for 12 hours to obtain the bio-oil, wherein the yield of the bio-oil is 31.7%; the blank group replaced the aqueous product of the hydrothermal liquefaction of soy protein with water, and the corresponding bio-oil yield was only 22.8%.
Example 2
The embodiment provides a method for hydro-thermally liquefying bio-oil by carbohydrate biomass, which comprises the following steps:
(1) adding 10g of pine biomass and 30g of chlorella hydrothermal liquefaction water-phase product into a reaction kettle and sealing the reaction kettle.
(2) And heating the reaction kettle to 260 ℃, keeping the temperature for 300min, stopping heating, and cooling the reaction kettle to room temperature.
(3) After the reaction kettle is cooled to room temperature, the gas is collected firstly, then the reaction kettle is opened, the product is collected by a glass cup, and a water phase is obtained by a reduced pressure filtration mode.
The kettle and the remaining solid product were then washed with ethyl acetate, and the mixture of ethyl acetate and solid product was placed in a beaker and sonicated for 30min in ultrasound.
(4) And filtering the product after ultrasonic extraction under reduced pressure to obtain solid residue, wherein the liquid phase part after filtration is a mixed phase of ethyl acetate and bio-oil, pouring the mixed phase into an extraction bottle, and distilling to recover ethyl acetate.
(5) Drying the product after removing the ethyl acetate in a drying oven for 12h to obtain the bio-oil, wherein the yield of the bio-oil is 30.3%; the blank group replaced the aqueous product of the hydrothermal liquefaction of soy protein with water, corresponding to a bio-oil yield of 21.1%.
Example 3
The embodiment provides a method for hydro-thermally liquefying bio-oil by carbohydrate biomass, which comprises the following steps:
(1) 5g of sawdust biomass and 50g of spirulina hydrothermal liquefaction water phase product are added into a reaction kettle and sealed.
(2) Heating the reaction kettle to 320 ℃, keeping the temperature for 100min, stopping heating, and cooling the reaction kettle to room temperature.
(3) After the reaction kettle is cooled to room temperature, the gas is collected firstly, then the reaction kettle is opened, the product is collected by a glass cup, and a water phase is obtained by a reduced pressure filtration mode.
The kettle and the remaining solid product were then washed with acetone, and the acetone and solid product mixture was placed in a beaker and sonicated for 30min in ultrasound.
(4) And filtering the product after ultrasonic extraction under reduced pressure to obtain solid residue, wherein the liquid phase part after filtration is a mixed phase of acetone and bio-oil, pouring the mixed phase into an extraction bottle, and distilling to recover the acetone.
(5) Putting the product after removing the acetone into a drying oven to be dried for 12 hours to obtain the bio-oil, wherein the yield of the bio-oil is 35.6%; the blank group replaced the water phase product of the hydrothermal liquefaction of spirulina with water, corresponding to a bio-oil yield of 25.4%.
Example 4
The embodiment provides a method for hydro-thermally liquefying bio-oil by carbohydrate biomass, which comprises the following steps:
(1) 5g of cellulose biomass and 45g of soybean protein hydrothermal liquefaction water phase product are added into a reaction kettle and sealed.
(2) Heating the reaction kettle to 280 ℃, keeping the temperature for 30min, then stopping heating, and cooling the reaction kettle to room temperature.
(3) After the reaction kettle is cooled to room temperature, the gas is collected firstly, then the reaction kettle is opened, the product is collected by a glass cup, and a water phase is obtained by a reduced pressure filtration mode.
The kettle and the remaining solid product were then washed with acetone, and the acetone and solid product mixture was placed in a beaker and sonicated for 30min in ultrasound.
(4) And filtering the product after ultrasonic extraction under reduced pressure to obtain solid residue, wherein the liquid phase part after filtration is a mixed phase of acetone and bio-oil, pouring the mixed phase into an extraction bottle, and distilling to recover the acetone.
(5) Putting the product after removing the acetone into a drying oven to be dried for 12 hours to obtain the bio-oil, wherein the yield of the bio-oil is 19.2%; the blank group replaced the aqueous product of the hydrothermal liquefaction of soy protein with water, corresponding to a bio-oil yield of 7.2%.
Comparative example 1
This comparative example provides a method for hydrothermal liquefaction of bio-oil from carbohydrate biomass, differing from example 1 in the reaction medium; the method specifically comprises the following steps: the aqueous product of the hydrothermal liquefaction of soy protein in example 1 was replaced with the aqueous product of the hydrothermal liquefaction of cow dung (protein content 11%).
The results show that: the yield of bio-oil obtained was only 24.5%. Thus, the aqueous phase product of the protein biomass after hydrothermal liquefaction is superior to that of biomass containing other nitrogen compounds.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, it is intended that all such modifications and alterations be included within the scope of this invention as defined in the appended claims.
Claims (10)
1.A method for hydrothermally liquefying bio-oil with carbohydrate biomass, comprising: performing hydrothermal liquefaction on carbohydrate biomass in a reaction medium at a certain temperature; the method is characterized in that the reaction medium is a water-phase product obtained after protein biomass is hydrothermally liquefied.
2. The method for the hydrothermal liquefaction of bio-oil by carbohydrate biomass as claimed in claim 1, wherein the main components of the aqueous phase product after the hydrothermal liquefaction of protein biomass except water comprise: nitrogen-containing compounds, phenolic compounds and ketone compounds;
wherein, calculated by water phase products except water, the nitrogen-containing compounds comprise ammonia, chain amide, amino acid, pyridine and indole, and account for 60-80 percent; the phenolic compound accounts for 1-8%; the ketone compound accounts for 3-15%.
3. The method of claim 2, wherein the protein content of the protein biomass is at least 50% or greater;
preferably, the proteinaceous biomass is selected from one or more of soy protein, chlorella or spirulina.
4. The method for hydrothermally liquefying bio-oil by using carbohydrate biomass as claimed in claim 3, wherein the mass ratio of the carbohydrate biomass to the aqueous phase product of the hydrothermal liquefaction of protein biomass is 1: 100-1: 3.
5. The method for the hydrothermal liquefaction of bio-oil from carbohydrate biomass according to claim 4, characterized in that the reaction conditions of the hydrothermal liquefaction are as follows: the temperature is 260-360 ℃, and the time is 1-300 min.
6. The method for the hydrothermal liquefaction of bio-oil with carbohydrate biomass as claimed in claim 5, wherein the hydrothermal liquefaction reaction is batch or continuous.
7. The method for hydrothermally liquefying bio-oil by using carbohydrate biomass as claimed in claim 6, wherein after the hydrothermal liquefaction reaction is finished, the obtained mixed solution is cooled, gas is collected, water phase is obtained by filtration, ultrasonic extraction is carried out, reduced pressure filtration, distillation and drying are carried out, and bio-oil is obtained.
8. The method for the hydrothermal liquefaction of bio-oil by carbohydrate biomass as claimed in claim 7, wherein the extractant used in the extraction is one of acetone, dichloromethane and ethyl acetate.
9. The method of claim 8, wherein the carbohydrate biomass is selected from the group consisting of cellulose, straw, pine, and sawdust.
10. The method for the hydrothermal liquefaction of bio-oil with carbohydrate biomass as claimed in claim 9, wherein the carbohydrate biomass is cellulose and the reaction medium is a soy protein hydrothermal liquefaction aqueous phase product; the mass ratio of the carbohydrate biomass to the reaction medium is 1: (9-10), conditions of hydrothermal liquefaction: the temperature is 280-285 ℃, and the time is 25-30 min;
or the carbohydrate biomass is straw, and the reaction medium is a soybean protein hydrothermal liquefaction water-phase product; the mass ratio of the carbohydrate biomass to the reaction medium is 1: (40-42), conditions of hydrothermal liquefaction: the temperature is 360-365 ℃, and the time is 8-10 min;
or the carbohydrate biomass is pine wood, and the reaction medium is a chlorella hydrothermal liquefaction water-phase product; the mass ratio of the carbohydrate biomass to the reaction medium is 1: (3-3.5), hydrothermal liquefaction conditions: the temperature is 260-265 ℃, and the time is 290-300 min;
or the carbohydrate biomass is sawdust, and the reaction medium is a spirulina hydrothermal liquefaction water-phase product; the mass ratio of the carbohydrate biomass to the reaction medium is 1: (10-11), conditions of hydrothermal liquefaction: the temperature is 320 ℃ and 330 ℃, and the time is 90-100 min.
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