CN110846070A - A kind of metal element aluminum is used as hydrogen source to carry out hydro-upgrading method to crude bio-oil - Google Patents

Abstract

The invention discloses a method for carrying out hydrogenation modification on crude bio-oil by using metal simple substance aluminum as a hydrogen source, which comprises the steps of uniformly mixing the crude bio-oil with the metal simple substance aluminum, water, tetrahydronaphthalene and a noble metal catalyst, and carrying out heating reaction at the temperature of 300-450 ℃ for 1-4 h. According to the invention, the online hydrogen production is realized through the reaction of the metal aluminum and the water, the crude bio-oil hydrodeoxygenation, denitrification and desulfurization can be realized by utilizing the high activity of the newly generated hydrogen free radicals, and the addition of high-pressure hydrogen is avoided, so that the requirements on equipment and potential safety hazards caused by hydrogen transportation and storage are reduced. Tetrahydronaphthalene is added in the reaction process, so that crude bio-oil can be diluted, carbon deposition generation is reduced, and a hydrogen transfer effect is achieved; the addition of tetralin also can lead the reaction product to be directly separated by centrifugation, thus avoiding the use of solvent.

Description

A kind of metal element aluminum is used as hydrogen source to carry out hydro-upgrading method to crude bio-oil

technical field

The present application relates to the field of biomass energy, and in particular, to a method for hydrogenating crude bio-oil with elemental aluminum as a hydrogen source.

Background technique

The traditional hydrogenation method is widely used as a common crude bio-oil treatment method, but at the same time, it also has problems such as high cost and low hydrogen reaction efficiency. Obtaining a cheap, readily available, high-quality, sufficient and fully suitable hydrogen source for the upgrading reaction system in the upgrading of crude bio-oil is one of the current problems to be solved. At present, there are also some researches on the catalytic hydrogenation process of crude bio-oil, which has been improved on the basis of the traditional method, and developed two stages of hydrogenation and upgrading process: first, pretreatment, crude bio-oil at a lower temperature (≤ 300°C) to carry out mild hydrotreating to convert the components with poor stability; and then carry out the traditional hydromodification method. With this two-stage hydrogenation process, the hydrogen pressure of the reaction was increased from 2.5 MPa in the first stage to 10 MPa in the second stage using a commercial Ni-Mo/γ-Al ₂ O ₃ catalyst at 500 °C. However, there are few reports on the exploration of cheap hydrogen sources in the upgrading process of crude bio-oil and its specific application in the upgrading of crude bio-oil.

SUMMARY OF THE INVENTION

The invention provides a method for hydrogenating crude bio-oil with elemental metal aluminum as a hydrogen source. ℃ heating the reaction for 1-4h.

Further, the weight ratio of crude bio-oil to metal element aluminum, water and tetralin is 1:(0.1-0.3):(0.5-1.5):(2-6). Preferably, the weight ratio of crude bio-oil to metal element aluminum, water, and tetralin is 1:0.21:0.85:4.

Further, the crude bio-oil is biomass thermochemically converted bio-oil; deionized water is selected for water.

Further, the noble metal catalyst is Pt/C, Ru/C, Rh/C, Pd/C and/or Ir/C; the addition amount of the noble metal catalyst is 1-10 wt.% of the bio-oil.

Further, the heating reaction is completed in the reaction kettle; before the heating reaction, the air in the reaction kettle is evacuated with argon; after the heating reaction is completed, the reaction product is cooled to room temperature, centrifuged at 10,000 rpm, and separated to obtain the modified oil.

The beneficial effects of the present invention include:

(1) On-line hydrogen production is achieved by the reaction of metal aluminum with water, and the hydrodeoxygenation, denitrification and desulfurization of crude bio-oil can be realized by utilizing the high activity of newly generated hydrogen radicals. At the same time, the addition of high-pressure hydrogen is avoided, thereby reducing the impact on equipment. It also avoids the safety hazards caused by hydrogen transportation and storage.

(2) adding tetralin in the reaction process can dilute the crude bio-oil to reduce carbon deposition, and can also play the role of transferring hydrogen; the addition of tetralin can also make the reaction product directly separated by centrifugation, avoiding the use of solvents .

Detailed ways

The present invention will be further illustrated and described below with reference to the embodiments, but the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the present invention and the embodiments, all other inventions and embodiments obtained by those of ordinary skill in the art without creative work fall within the protection scope of the present invention.

The experimental methods used in the following examples are conventional methods unless otherwise specified.

The materials, reagents, etc. used in the following examples can be obtained from commercial sources unless otherwise specified.

Example 1

Add 5g of aluminum powder and 20mL of deionized water into a 50mL reaction kettle, seal the reaction kettle, empty the reaction kettle with helium gas and fill it with 0.01MPa helium gas as the internal standard, react at 400 ° C for 2 hours, and quickly cool down. After reaching room temperature, the gas was collected into a 1 L gas test bag for gas phase detection, and the amount of hydrogen produced was 627.18 mmol.

Example 2

Add 0.21g aluminum powder and 0.85mL deionized water to a 50mL reaction kettle, seal the reaction kettle, empty the reaction kettle with helium gas and fill it with 0.01MPa helium gas as the internal standard, and react at 400 ° C for 2 hours, It was rapidly cooled to room temperature, and the gas was collected into a 1 L gas test bag for gas phase detection, and the amount of hydrogen produced was 27.61 mmol.

Example 3

Add 100g of fully dried chlorella and 200g of deionized water mixed slurry into a 1L stainless steel batch reactor, use argon to empty the air in the reactor, seal the reactor, and react at 350 ° C for 1 hour; the reaction ends , put the reactor into a room temperature water bath for cooling; when the reactor is cooled to room temperature, open the gas outlet valve of the reactor and discharge the gas of the reactor; then open the reactor, pour the reactant into a 1L beaker, then use 200mL of dichloromethane Rinse the reactor wall and pipeline, and transfer the rinse liquid to a 1L beaker; use a Buchner funnel to separate the liquid and solid residues, and use a separation funnel to separate the dichloromethane and water phases; use a rotary evaporator to remove the dichloromethane phase obtained from the separation The methylene chloride inside, and the final obtained substance is the crude bio-oil.

Example 4

Add 100g of fully dried crop straws (soybeans, corn, peanuts, rice, etc.) and 200g of deionized water mixed slurry into a 1L stainless steel batch reactor, use argon to empty the air in the reactor, seal the reactor, React at 350 ° C for 1 hour; after the reaction, put the reactor into a room temperature water bath for cooling; when the reactor is cooled to room temperature, open the gas outlet valve of the reactor and discharge the gas of the reactor; then open the reactor and pour the reactants into 1L Then use 200mL of dichloromethane to rinse the reactor wall and pipeline, and transfer the rinse to a 1L beaker; use a Buchner funnel to separate the liquid and solid residues, and use a separation funnel to separate the dichloromethane and water phases; In the dichloromethane phase, a rotary evaporator is used to remove the dichloromethane inside, and the final obtained material is the crude bio-oil.

Example 5

Add 100g of fully dried macroalgae (Cross vera, duckweed, etc.) and 200g of deionized water mixed slurry into a 1L stainless steel batch reactor, empty the reactor with argon, seal the reactor, and set it at 350 ℃. React at ℃ for 1 hour; after the reaction, put the reactor into a room temperature water bath for cooling; when the reactor is cooled to room temperature, open the gas outlet valve of the reactor and discharge the gas of the reactor; then open the reactor and pour the reactants into a 1L beaker Then, use 200mL of dichloromethane to rinse the reactor wall and pipeline, and transfer the rinse to a 1L beaker; use a Buchner funnel to separate the liquid and solid residues, and use a separation funnel to separate the dichloromethane and water phases; In the methyl chloride phase, the dichloromethane in the rotary evaporator is removed, and the final obtained substance is the crude bio-oil.

Example 6

1 g of crude bio-oil obtained in Example 3, 4 g of tetrahydronaphthalene, 0.85 g of deionized water, 0.21 g of aluminum powder, 0.1 g of Pt/C (Pt, 10 wt.%) were loaded into a 50 mL reaction kettle, mixed uniformly, and then The air in the reactor was evacuated with argon, and the sealed reactor was heated to 400° C. for reaction for 2 hours. After the reaction was completed, it was rapidly cooled to room temperature in ice water, the reactor was opened, and the reaction product was centrifuged at 10,000 rpm to separate and obtain the modified oil.

Example 7

1 g of crude bio-oil obtained in Example 3-5, 6 g of tetralin, 1.5 g of deionized water, 0.3 g of aluminum powder, and 0.1 g of Pt/C (Pt, 10 wt.%) were loaded into a 50 mL reaction kettle, and mixed uniformly , then the air in the reactor was evacuated with argon, the sealed reactor was heated to 400 ° C for 2 hours, and after the reaction was completed, it was rapidly cooled to room temperature in ice water, the reactor was opened, and the reaction product was centrifuged at 10,000 rpm to separate and obtain modified oil.

Example 8

1 g of crude bio-oil obtained in Example 3-5, 2 g of tetralin, 0.5 g of deionized water, 0.1 g of aluminum powder, and 0.1 g of Pt/C (Pt, 10 wt.%) were loaded into a 50 mL reaction kettle, and mixed uniformly , then the air in the reactor was evacuated with argon, the sealed reactor was heated to 400 ° C for 2 hours, and after the reaction was completed, it was rapidly cooled to room temperature in ice water, the reactor was opened, and the reaction product was centrifuged at 10,000 rpm to separate and obtain modified oil.

Example 9

1 g of crude bio-oil obtained in Example 3-5, 6 g of tetralin, 1.5 g of deionized water, 0.3 g of aluminum powder, and 0.1 g of Pt/C (Pt, 10 wt.%) were loaded into a 50 mL reaction kettle, and mixed uniformly , then the air in the reactor was evacuated with argon, the sealed reactor was heated to 300 ° C for 2 hours, and after the reaction was completed, it was rapidly cooled to room temperature in ice water, the reactor was opened, the reaction product was centrifuged at 10,000 rpm, and the modified oil was obtained by separation.

Example 10

1 g of crude bio-oil obtained in Example 3-5, 6 g of tetralin, 1.5 g of deionized water, 0.3 g of aluminum powder, and 0.1 g of Pt/C (Pt, 10 wt.%) were loaded into a 50 mL reaction kettle, and mixed uniformly , then the air in the reactor was evacuated with argon, the sealed reactor was heated to 450 ° C for 2 hours, and after the reaction was completed, it was rapidly cooled to room temperature in ice water, the reactor was opened, and the reaction product was centrifuged at 10,000 rpm to separate and obtain the modified oil.

The modified oil obtained in Example 6-10 was characterized, and its process was as follows:

Determination of elemental composition of modified oil: take 2.5 mg of modified oil, use Flash 2000 elemental analyzer to test C, H, N, O in the modified oil, and measure the corresponding peak area through the marking line established by standard sample in advance. Calculate and obtain the content (wt.%) of the corresponding element; use the TS-3000 fluorescence sulfur analyzer produced by Jiangsu Guochuang to test the S content in the modified oil, and use the standard line established in advance to measure the corresponding peak area. Calculated and obtained the content of S element (ppm); GC-MS test was carried out by PEGASUS 4D comprehensive two-dimensional gas chromatography time-of-flight mass spectrometer of American Leco Company. The gas chromatograph (GC×GC) model is Agilent 7890A, the first chromatographic column used is VF-17MS (30m×0.25mmID×0.25μm), and the second chromatographic column is polar column RXI-17 (1m×0.1 mmID×0.1μm). The samples were subjected to two-dimensional analysis, and the modified oil was diluted 20 times with chromatographically pure dichloromethane according to the mass fraction, and the injection volume was 1 μL. The ion source temperature is 250°C, the transmission wire temperature is 280°C, the inlet temperature is 300°C, the signal-to-noise ratio is 100, the test helium flow rate is 1mL/min, the splitless liner is used, the solvent delay is 240s, and the dichloromethane as the solvent is delayed. . The heating program was adopted: the initial temperature was kept at 40 °C for 3 min, and then the temperature was raised to 280 °C at 4 °C/min and held for 3 min, and the whole process was 3900 s. The mass spectrum acquisition rate is 100 spectra per second. For each substance, 10 substances with the highest similarity are selected from the mainlib and replib for identification. We default the similarity of more than 700 to the correct substances.

It can be seen from the above characterization results that the element composition of the upgraded oil obtained by the catalytic hydroprocessing in Example 6 is: C: 89.36wt.%, N: 0.80wt.%, H: 9.15wt.%, S: 204.66 ppm; the molecular components in the modified oil are as follows: aromatic hydrocarbons: 87.50%, saturated hydrocarbons: 1.39%, unsaturated hydrocarbons: 8.80%, lipids: 0.55%, ketones: 0.12%, N-containing components: 0.02%, O-containing Composition: 0.52%, containing N, O composition: 0.88%.

The element composition in the modified oil obtained by catalytic hydroprocessing in Example 7-10 is: C: 85.32-91.54wt.%, N: 0.3-1.2wt.%, H: 8.72-9.87wt.%, S: 89- 240ppm; the molecular components in the modified oil are: aromatic hydrocarbons: 85.23-90.21%, saturated hydrocarbons: 0.32-4.23%, unsaturated hydrocarbons: 4.35-10.25%, fats: 0.15-0.89%, ketones: 0.08-0.24%, N-containing component: 0.01-0.04%, O-containing component: 0.31-0.75%, N, O-containing component: 0.46-0.97%.

Claims (10)

1. a kind of metal element aluminum carries out hydrogenation upgrading method to crude bio-oil as hydrogen source, it is characterized in that comprising the steps: crude bio-oil is mixed with metal element aluminum, water, tetralin and noble metal catalyst, 300- The reaction was heated at 450°C for 1-4h. 2. elemental metal aluminum according to claim 1 carries out hydro-upgrading method to crude bio-oil as hydrogen source, it is characterized in that, the weight ratio of described crude bio-oil and elemental metal aluminum, water, tetralin is 1 : (0.1 to 0.3): (0.5 to 1.5): (2 to 6). 3. elemental metal aluminum according to claim 2 carries out hydrogenation upgrading method to crude bio-oil as hydrogen source, it is characterized in that, the weight ratio of described crude bio-oil and elemental metal aluminum, water, tetralin is 1 :0.21:0.85:4. 4. The method for hydro-upgrading crude bio-oil according to any one of claims 1-3, wherein the crude bio-oil is a biomass thermochemically converted bio-oil as a hydrogen source. 5 . The method for hydro-upgrading crude bio-oil according to any one of claims 1 to 3, wherein elemental metal aluminum is used as a hydrogen source, wherein the water is deionized water. 6. metal element aluminum according to any one of claim 1-3 carries out hydrogenation upgrading method to crude bio-oil as hydrogen source, it is characterized in that, described noble metal catalyst is Pt/C, Ru/C, Rh/ C, Pd/C and/or Ir/C. 7 . The method for hydro-upgrading crude bio-oil using elemental metal aluminum as a hydrogen source according to claim 6 , wherein the amount of the noble metal catalyst added is 1-10 wt. % of the bio-oil. 8 . 8 . The metal elemental aluminum according to claim 1 is used as a hydrogen source to carry out a hydro-upgrading method for crude bio-oil, wherein the heating reaction is completed in a reactor. 9. The metal element aluminum according to claim 8 is used as the hydrogen source to carry out the hydrogenation upgrading method to crude bio-oil, it is characterized in that, before the described heating reaction, the air in the reactor is evacuated with argon. 10. elemental metal aluminum according to claim 8 is used as hydrogen source to carry out hydrogenation upgrading method to crude bio-oil, it is characterized in that, after described heating reaction finishes, be cooled to room temperature, centrifugal reaction product of 10000rpm, separation can obtain Modified oil.