CN107163973B - A kind of biomass is in situ for liquefaction of hydrogen method for producing oil - Google Patents

Abstract

The present invention relates to a kind of new methods of biomass by hydro-thermal liquefaction bio oil processed, are reacted with aluminium-water production hydrogen for hydrogen source, and collaboration corn stover catalytic liquefaction prepares bio oil, and quality of bio-oil can be improved, belong to environmental protection and field of new energy technologies.The present invention is reacted with aluminium-water production hydrogen for hydrogen source, corn stover catalytic liquefaction is cooperateed with to prepare bio oil, aluminum-water reaction produces hydrogen and biomass by hydro-thermal liquefaction while carrying out, hydrogen supply in situ is modified purified during biomass liquefying, it can effectively reduce bio oil oxygen content, calorific value is improved, achievees the purpose that improve quality of bio-oil.

Description

A kind of biomass in-situ hydrogen supply liquefaction method for oil production

Technical field:

The invention relates to a new method for preparing bio-oil by hydrothermal liquefaction of biomass. The hydrogen-producing reaction of aluminum and water is used as a hydrogen supply source, and the bio-oil is prepared by catalyzing liquefaction of biomass materials, which can improve the quality of the bio-oil; it belongs to environmental protection and New energy technology field.

Background technique:

With the decreasing reserves of fossil fuels such as petroleum and the increasingly serious environmental pollution problems, research and development of new technologies for petroleum alternative fuels is of strategic significance for alleviating my country's petroleum energy crisis and improving the serious environmental pollution problems. Biomass is the only renewable energy that can be converted into liquid fuels, and has the advantages of huge yield, storability and carbon cycle.

Biomass utilization mainly includes physical transformation technology, biochemical transformation technology, and thermochemical transformation technology. Physical conversion technology is mainly made into briquette fuel directly by adding additives and external compression. Biochemical transformation techniques mainly use enzymes and microorganisms to degrade biomass, such as fermentation. Thermochemical conversion technologies degrade biomass by heating, such as pyrolysis and liquefaction. Pyrolysis is a thermal conversion technology that degrades organic matter into small molecular substances in an inert atmosphere. The main pyrolysis products are bio-oil, charcoal, tar and pyrolysis gas. It is an important part of the current biomass thermal conversion technology. Liquefaction is a thermal conversion method that has emerged in recent years. Biomass liquefaction technology refers to the technology of liquefying biomass to produce liquid products under the conditions of high pressure, certain temperature and the presence of solvents, catalysts, etc., usually using water as the reaction medium, so it is also called hydrothermal liquefaction.

Bio-oil obtained by liquefaction of biomass has the advantages of safety and cleanliness, and has good research value, so it has received extensive attention. However, the disadvantages of high oxygen content and low calorific value of bio-oil make it difficult to burn directly on existing equipment or to mix with fossil fuel gasoline and diesel. Therefore, bio-oil needs to be modified and refined, and catalytic hydrogenation is currently the most effective and most widely used modification method. According to the different sources of hydrogen in the catalytic hydrogenation process, it can be divided into direct hydrogenation and in-situ hydrogen supply. Industrial hydrogen is mostly used for direct hydrogen supply, and the reaction needs to be carried out under a certain hydrogen pressure (4Mpa). However, this method has problems of high cost and high risk in the process of hydrogen production, transportation and storage. In-situ hydrogen supply is a method in which hydrogen is generated by the hydrolysis and thermochemical reaction of a hydrogen-donating agent, and hydrogen is directly added in the liquefaction process. In situ hydrogen supply has become the most concerned method in bio-oil modification research because it can avoid many problems of direct hydrogen supply. In-situ hydrogen donors mostly use salt-based inorganic hydrogen donors and organic hydrogen donors such as tetralin and small-molecule liquid alcohols, but there are generally problems such as low hydrogen production, and some hydrogen donors are harmful to the environment. Aluminum is the most abundant metal on earth. The hydrolysis reaction of aluminum can not only generate hydrogen (theoretical hydrogen production is 1244mL/g (Al)), but also release energy, and the reaction product is harmless to the environment. Reactions such as aluminum-water and zinc-water have been used in the hydrogenation of coal, asphalt and model compounds under supercritical water. When zinc and aluminum are oxidized, the hydrogen produced is used for the hydrogenation of organics. However, there are few experimental studies on the in-situ hydrogen supply method used in the process of biomass hydrothermal liquefaction.

SUMMARY OF THE INVENTION

In view of the high cost and high risk of direct hydrogen supply, the insufficient hydrogen supply efficiency of traditional in-situ hydrogen supply agents and the environmental harm, a novel method of in-situ hydrogen supply from biomass to liquefy bio-oil was proposed. The invention uses the hydrogen production reaction of aluminum and water as the hydrogen supply source, and cooperates with the catalytic liquefaction of corn stover to prepare bio-oil. The hydrogen production by the reaction of aluminum water and the hydrothermal liquefaction of biomass are carried out at the same time, and the in-situ hydrogen supply is modified and refined in the process of biomass liquefaction. It can effectively reduce the oxygen content of bio-oil, increase the calorific value, and achieve the purpose of improving the quality of bio-oil.

A kind of biomass in-situ hydrogen supply liquefaction oil production method, the method comprises the following steps: (1) weigh the mixture of 10-15g biomass powder and hydrogen supply agent, 0.1-0.3g catalyst are respectively poured into the reaction kettle, wherein The amount of hydrogen supply agent added is 10%-40% of the mass of biomass powder, and then 100-150mL of deionized water is added to the reactor; (2) Check and clean the dust and other foreign matter in the sealing ring of the reactor, and make sure there is no foreign matter Then, raise the kettle body to close the upper and lower parts of the reactor and tighten the screws symmetrically; (3) Check whether the vent valve of the reactor is dredged, and after confirming that its ventilation condition is good, purge the reactor with nitrogen for 3-5min to discharge the air , after purging, close the vent valve of the reaction kettle, disconnect the nitrogen and pass cooling water to the magnetic stirrer; (4) open the computer heating program, set the jacket temperature to 400-500 ° C, and set the reaction temperature to 280-380 ° C, The total pressure is 5-30Mpa, the rotating speed of the magnetic stirrer is set to 300r/min, the temperature is raised to the set reaction temperature and the reaction is ended after maintaining the temperature for 1-90min; (5) after the reaction is completed, the reaction program is first stopped, and the jacket and The temperature in the reaction kettle is set to 0°C, the jacket is removed and the reaction kettle is slowly cooled down with a low-power fan. When the reaction kettle is cooled to about 25°C, the cooling can be stopped; (6) Open the exhaust valve and collect the inside of the kettle. Remaining gas, the reaction kettle can be disassembled when the pressure shows zero; (7) pour out the solid-liquid mixture in the kettle, obtain water phase and solid 1 after filtration, wherein the water phase part is added with dichloromethane and extracted to the water phase Clarification to obtain the soluble part of dichloromethane, and the soluble part of dichloromethane was subjected to rotary evaporation at 40 ° C to obtain oil 1; the above solid 1 was washed with acetone and ethanol respectively until the liquid was clarified to obtain organic phase 2; then use absolute ethanol and Acetone rinses the reaction still wall, agitator and the pipeline in the still successively to obtain the organic phase mixture after filtration to obtain the organic phase 1 and solid 2. After the organic phases 1 and 2 are mixed, the oil 2 is obtained after the organic phase 1 and 2 are mixed under reduced pressure and rotary evaporation at 85°C, and the oil 1 is obtained. The sum of and oil 2 is defined as the bio-oil obtained in this experiment; the sum of solid 1 and solid 2 is defined as the residue, which is weighed after being placed in an oven at 105° C. for 12 hours.

The hydrogen donor is aluminum powder.

The biomass powder is one or a combination of corn straw, rice straw and wood chips. The particle size of the biomass powder is 0.25 mm.

The catalyst is a dispersed catalyst NiS-MoS.

The nitrogen described in step 3 is high-purity nitrogen.

The ethanol and acetone described in step 6 are of analytical grade.

Beneficial effects of the present invention:

1. The biomass raw materials used in the present invention belong to renewable energy sources, which are widely available and do not require high energy-consuming pretreatment, and can be directly utilized.

2. The present invention liquefies biomass into liquid fuel, which can effectively solve the problem of recycling and utilization of agricultural and forestry wastes and slow down the environmental pollution caused by biomass burning. It can also alleviate the shortage of fossil energy such as petroleum to a certain extent.

3. The composition of bio-oil is so complicated that it can contain hundreds of organic compounds. Its high oxygen content causes the bio-oil to be unstable and has a relatively low calorific value, thus affecting the large-scale application of bio-oil. This study can significantly improve the yield of bio-oil and reduce the oxygen content of bio-oil, and the deoxygenation efficiency can reach 51.6%.

4. The aluminum-based hydrogen-donating agent not only has a wide range of sources and is non-toxic, but also produces Al ₂ O ₃ or AlO(OH), which is environmentally friendly.

5. The present invention improves and supplements the selection of hydrogen supplying agents in the biomass in-situ hydrogen supplying liquefaction technology.

Description of drawings

Fig. 1 is the flow chart of the overall steps of the method proposed by the present invention;

Detailed ways:

Example 1

Add 15g corn stalk powder, 0g NiS-MoS, 0g aluminum powder, then add 150mL deionized water, mix evenly, and seal the reaction kettle; before heating up each experiment, purge with high-purity nitrogen (99.99%) for 5min to remove air, and stir magnetically. The speed of the reactor was set to 100 r/min and gradually increased to 300 r/min; the temperature in the kettle was set to 370 °C, and the reaction residence time was set to 60 min; after the reaction, the jacket was removed, cooled to room temperature, and the gas was analyzed with an infrared online gas analyzer. Its composition was measured, and then the reactor was opened. Pour out the solid-liquid mixture in the kettle, obtain water phase and solid 1 after filtration; rinse the reactor wall, agitator and pipeline in the kettle successively with absolute ethanol and acetone, after the obtained mixture is filtered, obtain organic phase 1 and solid 2 The aqueous phase was extracted with dichloromethane to obtain the dichloromethane soluble part, and the oil 1 was obtained by rotary evaporation at 40°C; the solid 1 was washed with acetone and ethanol to obtain the organic phase 2, and the organic phases 1 and 2 were mixed and then decompressed at 85°C. Oil 2 was obtained by rotary evaporation, and the sum of oil 1 and oil 2 was defined as the bio-oil obtained in this experiment; the sum of solid 1 and solid 2 was defined as the residue, which was weighed after being placed in an oven at 105 °C for 12 hours. The oil yield was 18.20%. The oxygen content of bio-oil is 26.98%.

Example 2

The oil production rate of bio-oil prepared by catalytic liquefaction of biomass material was investigated without adding hydrogen-donating agent;

Add 15g of corn stalk powder, 0.3g of NiS-MoS, 0g of aluminum powder, and then add 150mL of deionized water, mix well, and seal the reactor; before heating up each experiment, high-purity nitrogen (99.99%) was used to purge for 5min to remove air. The rotational speed of the magnetic stirrer was set to 100 r/min and gradually increased to 300 r/min; the temperature in the kettle was set to 370 °C, and the reaction residence time was set to 60 min. After the reaction was completed, the jacket was removed, cooled to room temperature, and the gas composition was measured with an infrared online gas analyzer, and then the reaction kettle was opened. Pour out the solid-liquid mixture in the kettle, obtain water phase and solid 1 after filtration; rinse the reactor wall, agitator and pipeline in the kettle successively with absolute ethanol and acetone, after the obtained mixture is filtered, obtain organic phase 1 and solid 2 The aqueous phase was extracted with dichloromethane to obtain the dichloromethane soluble part, and the oil 1 was obtained by rotary evaporation at 40°C; the solid 1 was washed with acetone and ethanol to obtain the organic phase 2, and the organic phases 1 and 2 were mixed and then decompressed at 85°C. Oil 2 was obtained by rotary evaporation, and the sum of oil 1 and oil 2 was defined as the bio-oil obtained in this experiment; the sum of solid 1 and solid 2 was defined as the residue, which was weighed after being placed in a 105°C oven for 12 hours. In this experiment, the yield of bio-oil was 20.99%, and the oxygen content of bio-oil was 16.37%.

Example 3

Add 15g corn stalk powder, 0.3g NiS-MoS, 1.5g aluminum powder, then add 150mL deionized water, mix evenly, and seal the reactor; before heating up each experiment, use high-purity nitrogen (99.99%) to purge for 5min to remove air, . The rotational speed of the magnetic stirrer was set to 100 r/min and gradually increased to 300 r/min; the temperature in the kettle was set to 370 °C, and the reaction residence time was set to 60 min. After the reaction was completed, the jacket was removed, cooled to room temperature, and the gas composition was measured with an infrared online gas analyzer, and then the reaction kettle was opened. Pour out the solid-liquid mixture in the kettle, obtain water phase and solid 1 after filtration; rinse the reactor wall, agitator and pipeline in the kettle successively with absolute ethanol and acetone, after the obtained mixture is filtered, obtain organic phase 1 and solid 2 The aqueous phase was extracted with dichloromethane to obtain the dichloromethane soluble part, and the oil 1 was obtained by rotary evaporation at 40°C; the solid 1 was washed with acetone and ethanol to obtain the organic phase 2, and the organic phases 1 and 2 were mixed and then decompressed at 85°C. Oil 2 was obtained by rotary evaporation, and the sum of oil 1 and oil 2 was defined as the bio-oil obtained in this experiment; the sum of solid 1 and solid 2 was defined as the residue, which was weighed after being placed in a 105°C oven for 12 hours. The oil production rate in this experiment was 22.30%, and the oxygen content of bio-oil was 13.06%.

Example 4

Add 15g of corn stalk powder, 0.3g of NiS-MoS, 3g of aluminum powder, and then add 150mL of deionized water, mix evenly, and seal the reaction kettle; high-purity nitrogen (99.99%) is used to purge for 5min to remove air before heating in each experiment. The rotational speed of the magnetic stirrer was set to 100 r/min and gradually increased to 300 r/min; the temperature in the kettle was set to 370 °C, and the reaction residence time was set to 60 min. After the reaction was completed, the jacket was removed, cooled to room temperature, and the gas composition was measured with an infrared online gas analyzer, and then the reaction kettle was opened. Pour out the solid-liquid mixture in the kettle, obtain water phase and solid 1 after filtration; rinse the reactor wall, agitator and pipeline in the kettle successively with absolute ethanol and acetone, after the obtained mixture is filtered, obtain organic phase 1 and solid 2 The aqueous phase was extracted with dichloromethane to obtain the dichloromethane soluble part, and the oil 1 was obtained by rotary evaporation at 40°C; the solid 1 was washed with acetone and ethanol to obtain the organic phase 2, and the organic phases 1 and 2 were mixed and then decompressed at 85°C. Oil 2 was obtained by rotary evaporation, and the sum of oil 1 and oil 2 was defined as the bio-oil obtained in this experiment; the sum of solid 1 and solid 2 was defined as the residue, which was weighed after being placed in an oven at 105 °C for 12 hours. The oil rate was 25.88%, and the oxygen content of bio-oil was 13.88%.

Example 5

Add 15g of corn stalk powder, 0.3g of NiS-MoS, 4.5g of aluminum powder, and then add 150mL of deionized water, mix evenly, and seal the reaction kettle; high-purity nitrogen (99.99%) is used for purging for 5 minutes before the temperature of each experiment to remove air. The rotating speed of the magnetic stirrer was set to 100r/min and gradually increased to 300r/min; the temperature in the kettle was set to 370°C, and the reaction residence time was set to 60min; after the reaction was completed, the jacket was removed, cooled to room temperature, and the gas used infrared online gas The analyzer measures its composition, and then the reactor is opened. Pour out the solid-liquid mixture in the kettle, obtain water phase and solid 1 after filtration; rinse the reactor wall, agitator and pipeline in the kettle successively with absolute ethanol and acetone, after the obtained mixture is filtered, obtain organic phase 1 and solid 2 The aqueous phase was extracted with dichloromethane to obtain the dichloromethane soluble part, and the oil 1 was obtained by rotary evaporation at 40°C; the solid 1 was washed with acetone and ethanol to obtain the organic phase 2, and the organic phases 1 and 2 were mixed and then decompressed at 85°C. Oil 2 was obtained by rotary evaporation, and the sum of oil 1 and oil 2 was defined as the bio-oil obtained in this experiment; the sum of solid 1 and solid 2 was defined as the residue, which was weighed after being placed in an oven at 105 °C for 12 hours. The oil rate was 26.54%. The oxygen content of bio-oil is 14.05%.

Example 6

Add 15g corn stalk powder, 0.3g NiS-MoS, 6g aluminum powder, then add 150mL deionized water, mix evenly, and seal the reaction kettle; high-purity nitrogen (99.99%) was used for purging for 5 minutes before heating up in each experiment to remove air. The stirring speed was set to 100r/min and gradually increased to 300r/min; the temperature in the kettle was set to 370°C, and the reaction residence time was set to 60min; after the reaction, the jacket was removed, cooled to room temperature, and the gas was analyzed by infrared online gas analysis. instrument to measure its composition, and then open the reactor. Pour out the solid-liquid mixture in the kettle, obtain water phase and solid 1 after filtration; rinse the reactor wall, agitator and pipeline in the kettle successively with absolute ethanol and acetone, after the obtained mixture is filtered, obtain organic phase 1 and solid 2 The aqueous phase was extracted with dichloromethane to obtain the dichloromethane soluble part, and the oil 1 was obtained by rotary evaporation at 40°C; the solid 1 was washed with acetone and ethanol to obtain the organic phase 2, and the organic phases 1 and 2 were mixed and then decompressed at 85°C. Oil 2 was obtained by rotary evaporation, and the sum of oil 1 and oil 2 was defined as the bio-oil obtained in this experiment; the sum of solid 1 and solid 2 was defined as the residue, which was weighed after being placed in an oven at 105 °C for 12 hours. The oil yield was 23.26%. The oxygen content of bio-oil is 13.53%.

Example 7

Add 15g corn stalk powder, 0g NiS-MoS, 0g aluminum powder, then add 150mL deionized water, mix evenly, and seal the reaction kettle; before heating up each experiment, purge with high-purity nitrogen (99.99%) for 5min to remove air, and stir magnetically. The speed of the reactor was set to 100 r/min and gradually increased to 300 r/min; the temperature in the kettle was set to 370 °C, and the reaction residence time was set to 60 min; after the reaction, the jacket was removed, cooled to room temperature, and the gas was analyzed with an infrared online gas analyzer. Its composition was measured, and then the reactor was opened. Pour out the solid-liquid mixture in the kettle, obtain water phase and solid 1 after filtration; rinse the reactor wall, agitator and pipeline in the kettle successively with absolute ethanol and acetone, after the obtained mixture is filtered, obtain organic phase 1 and solid 2 The aqueous phase was extracted with dichloromethane to obtain the dichloromethane soluble part, and the oil 1 was obtained by rotary evaporation at 40°C; the solid 1 was washed with acetone and ethanol to obtain the organic phase 2, and the organic phases 1 and 2 were mixed and then decompressed at 85°C. Oil 2 was obtained by rotary evaporation, and the sum of oil 1 and oil 2 was defined as the bio-oil obtained in this experiment; the sum of solid 1 and solid 2 was defined as the residue, which was weighed after being placed in an oven at 105 °C for 12 hours. The oil yield was 18.20%. The oxygen content of bio-oil is 26.98%.

Conclusion: After adding aluminum powder and catalyst, the oil production rate increased, and the oxygen content of bio-oil decreased significantly, indicating that the addition of aluminum powder and catalyst helped to increase the yield of bio-oil and improve the physicochemical properties of bio-oil.

Claims (5)

1. a kind of biomass is in situ for liquefaction of hydrogen method for producing oil, which is characterized in that method includes the following steps: (1) weighs 10- The mixture of 15g powdered biomass and hydrogen supply agent, 0.1-0.3g catalyst pour into reaction kettle respectively, wherein hydrogen supply agent additive amount For the 10%-40% of powdered biomass quality, then the addition deionized water 100-150mL into reaction kettle；(2) it checks and clears up anti- It answers the dust and other foreign matters in kettle sealing ring, after determining foreign, increase autoclave body, closes the division of reaction kettle top and the bottom simultaneously symmetrical Screwing screw；(3) it checks whether reaction kettle breather valve is dredged, after determining that its aeration status is good, purges reaction kettle with nitrogen Air is discharged in 3-5min, and purging, which finishes, closes reaction kettle gas valve, disconnects nitrogen and leads to cooling water to magnetic stirring apparatus；(4) Computer temperature program is opened, sets jacket temperature as 400-500 DEG C, reaction temperature is set as 280-380 DEG C, total pressure 5- 30Mpa, magnetic stirring apparatus revolving speed are set as 300r/min, are warming up to after keeping temperature 1-90min after setting reaction temperature and tie Shu Fanying；(5) after reaction, stop response procedures first, collet and reactor temperature are set as 0 DEG C, remove collet And make reaction kettle slow cooling with small-power fan, when reaction kettle is cooled to 25 DEG C or so, it can stop cooling down；(6) it opens Exhaust valve collects residual gas in kettle, i.e. removable reaction kettle when pressure is shown as zero；(7) the solid-liquid mixing in kettle is poured out Object obtains water phase and solid 1 after filtering, and wherein aqueous portion is added methylene chloride and is extracted to water phase clarification, obtains dichloromethane The soluble fraction of methylene chloride is obtained oil 1 through 40 DEG C of rotary evaporations by alkane soluble fraction；Above-mentioned solid 1 uses acetone and second respectively Alcohol, which is rinsed to liquid, to be clarified to obtain organic phase 2；Reaction kettle wall, blender and kettle inner tube are successively rinsed with dehydrated alcohol and acetone again Line after obtaining mixture of organic phase filtering, obtains organic phase 1 and solid 2, and organic phase 1,2 is steamed after mixing through 85 DEG C of decompression rotations Oil 2 is obtained after hair, the sum of oil 1 and oily 2 is defined as the bio oil that this experiment obtains；The sum of solid 1 and solid 2 is defined as residue, It is placed in 105 DEG C of baking ovens and weighs after 12h；The hydrogen supply agent is aluminium powder.

2. a kind of biomass according to claim 1 is in situ for liquefaction of hydrogen method for producing oil, which is characterized in that the biomass Powder is corn stover, one of rice straw, sawdust or combination powder.The partial size of the powdered biomass is 0.25mm.

3. a kind of biomass according to claim 1 is in situ for liquefaction of hydrogen method for producing oil, which is characterized in that the catalysis Agent is disperse type catalyzer NiS-MoS.

4. a kind of biomass according to claim 1 is in situ for liquefaction of hydrogen method for producing oil, which is characterized in that described in step 3 Nitrogen is high pure nitrogen.

5. a kind of biomass according to claim 1 is in situ for liquefaction of hydrogen method for producing oil, which is characterized in that described in step 6 Ethyl alcohol and acetone be to analyze pure grade.