RU2823286C1 - Method of producing benzene and toluene by catalytic deoxygenation of organic fraction of liquid pyrolysis products of plant biomass - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing benzene and toluene by catalytic deoxygenation of an organic fraction of liquid products of pyrolysis of plant biomass. This method involves single-step processing in an autoclave reactor at pressure of 1.5±0.5 MPa, temperature of 270±5 °C, using a catalyst containing transition metal oxides. Method uses a solvent selected from propanol-2, ethanol, methanol, in a supercritical state, as well as a deoxygenation catalyst prepared by hydrothermal deposition, containing 1±0.25 wt.% of a transition or noble metal selected from Ni, Ru and Pd, and 99±0.25 wt.% of carrier, hypercrosslinked polystyrene. In the process of deoxygenation, a nitrogen-hydrogen mixture with hydrogen content of 20±5 vol.%, and the process is carried out for 60±5 minutes while stirring at 1,200±100 rpm. Amount of catalyst is 0.06–0.429 g, the ratio of pyrolysis products to catalyst is 30±5:1 wt.pts. Deoxygenation catalyst is reduced for 3±0.5 hours at temperature of 300±5 °C.

EFFECT: high rate and degree of deoxygenation, high output of products, reduced consumption of hydrogen, as well as reduced formation of coke and, as a result, reduced degree of catalyst deactivation.

3 cl, 2 tbl, 57 ex

Description

The invention relates to the chemical industry, namely to the field of obtaining hydrocarbons of the aromatic fraction through the catalytic deoxygenation of the organic fraction of liquid products obtained by pyrolysis of renewable raw materials of plant origin, and can be used at chemical and oil refining industries to produce hydrocarbon fuels.

The organic fraction of liquid products of pyrolysis of plant biomass includes hydrocarbons, oxygen-containing compounds and small amounts of nitrogen- and sulfur-containing substances. To effectively use the organic fraction of liquid products of pyrolysis of plant biomass as transport fuel, it is necessary to improve their chemical and physical properties through catalytic deoxygenation, which consists in removing oxygen from oxygen-containing compounds.

There is a known method for the deoxygenation of organic oxygen products of rapid pyrolysis of plant biomass (RU, No. 2335340, IPC B01J 23/89, 10.10.2008), which is carried out in one stage at a hydrogen pressure of less than 3.0 MPa, a temperature of 250-320°C in the presence of a catalyst formed by sequential or simultaneous precipitation of transition metal hydroxides or carbonates in the presence of a stabilizing carrier, followed by aging in the mother solution, filtration and reduction with hydrogen at a temperature of 300-350°C. The deoxygenation process is carried out in a flow reactor mainly at a temperature of 200-300°C and a hydrogen pressure of 1.0-2.5 MPa with a space velocity (LHSV) of the oxygen-containing liquid equal to 0.3-2.0 ml/ml cat/h.

There is a known method for the deoxygenation of organic oxygen products from the processing of plant biomass (RU, No. 2472584, IPC B01J 23/755, 01/20/2013), which is carried out in one stage at a hydrogen pressure of 0.5-20 MPa, a temperature of 250-320°C in the presence of a catalyst, containing Ni in reduced form and other transition metals, as well as up to 15 wt. % phosphorus in the form of phosphides. The deoxygenation process is carried out in the following types of reactors: flow-through with a fixed bed of catalyst and a gaseous state of the initial reagents and reaction products, autoclave with intensive stirring of the catalyst in the liquid phase of the organic oxygen component.

There is a known method for deoxygenation of organooxygen products of processing plant biomass (Roldugina E.A., Hydroenrichment of bio-oil and its components on heterogeneous catalysts containing noble metals. Dissertation for Candidate of Chemical Sciences, Moscow, M.V. Moscow State University Lomonosova, 2019, 171 pp.), which is carried out in one stage in methanol at a hydrogen pressure of 5.0-8.5 MPa, temperature 200-300°C, substrate: metal ratio 160:1 for 3-6 hours. the presence of a catalyst containing Ru in reduced form and silicate material Al-HMS as a carrier.

There is a known method for deoxygenation of oxygen-containing products of processing plant biomass (Khromova S.A. Study of the processes of catalytic deoxygenation of model compounds of bio-oil. Abstract of the dissertation for the candidate of chemical sciences, Novosibirsk, Institute of Chemical Engineering named after G.K. Boreskov SB RAS, 2010, 19 p.), which is carried out in one stage at a hydrogen pressure of 0.5 MPa, a temperature of 300°C in the presence of a catalyst containing 16 wt. % Ni in reduced form, 2 wt. % Cu in reduced form and 82 wt. % δ-Al ₂ O ₃ .

However, the presented methods for producing aromatic hydrocarbons are characterized by:

- the use of high temperatures, which increases the energy costs of the process and causes the likelihood of carbon losses due to the possible occurrence of the cracking process;

- high consumption of hydrogen, which increases the capital costs of the process and leads to a decrease in the yield of aromatic compounds due to their hydrogenation;

- complex composition of the catalyst containing at least 3 components;

- low yield of benzene and toluene due to a large number of side processes.

The closest analogue is the method of deoxygenation of oxygen-containing products of processing plant biomass (RU, No. 2440847, IPC B01J 23/755, 01/27/2012), which is carried out in one stage at a hydrogen pressure of 0.5-20 MPa, temperature 250-320° C in the presence of a catalyst, which is a complex composite containing mixed oxides of transition metals (Ni, Fe, Co, Pd, Cu, Ga, In, Tl, W, Mo) and a stabilizing additive (Al ₂ O ₃ , SiO ₂ , ZrO ₂ , CeO ₂ , TiO ₂ , Cr ₂ O ₃ , MoO ₂ , WO ₂ , V ₂ O ₅ , MnO ₂ ). The problem of achieving high degrees of deoxygenation at a higher substrate/catalyst ratio is solved by creating and using a catalyst for the deoxygenation of organic oxygen products from the processing of plant biomass, which is a complex composite containing at least 3 different metals, one of which is nickel. The degree of deoxygenation of the products of pyrolysis of plant biomass by analogue when using an autoclave reactor in the presence of a pre-reduced catalyst containing, wt. %: 60 Ni, 5 Cu, 5 Fe and 30 CeO ₂ -ZrO ₂ , at 350°C and a hydrogen pressure of 2.0 MPa is 70%. The selectivity to benzene and toluene under these conditions is 39%.

However, this method, as well as other methods discussed above for the production of aromatic hydrocarbons, is characterized by the use of high temperatures and high pressures of hydrogen, which significantly increases the cost of the process, as well as the multicomponent composition of the catalyst, which complicates the process.

The technical problem solved when creating the invention is the development of a method for converting the organic fraction of the products of pyrolysis of plant biomass, which minimizes the formation of solid products and deactivation of the catalyst, reduces hydrogen consumption and maximizes the yield of benzene and toluene.

The technical result of the invention is:

1) Increasing the rate and degree of deoxygenation of the organic fraction of plant biomass pyrolysis products.

2) Increasing the yield of products with high added value and high energy potential (benzene and toluene).

3) Reducing hydrogen consumption during deoxygenation of the organic fraction of plant biomass pyrolysis products.

4) Reduced coke formation and, as a consequence, a decrease in the degree of catalyst deactivation.

The solution to the problem posed and the stated technical result are achieved due to the fact that the method for producing benzene and toluene by catalytic deoxygenation of the organic fraction of liquid products of pyrolysis of plant biomass, including one-stage processing in an autoclave reactor at a pressure of 1.5 ± 0.5 MPa, temperature 270 ± 5 °C, using a catalyst containing transition metal oxides, additionally includes the use of a solvent selected from 2-propanol, ethanol, methanol, in a supercritical state, the use of a deoxygenation catalyst prepared by hydrothermal precipitation containing 1 ± 0.25 wt. % transition or noble metal selected from Ni, Ru and Pd, and 99 ± 0.25 wt. % of the carrier of over-residue polystyrene, in the deoxygenation process a nitrogen-hydrogen mixture with a hydrogen content of 20±5 vol.% is used, the process is carried out for 60±5 minutes with stirring at a speed of 1200±100 rpm, while the amount of catalyst is 0.06 -0.429 g, the ratio of pyrolysis products/catalyst is 30±5:1 wt. parts, the deoxygenation catalyst is reduced for 3±0.5 hours at a temperature of 300±5°C.

The method preferably uses 2-propanol as a solvent and Pd as a transition or noble metal in the deoxygenation catalyst.

The proposed method for producing benzene and toluene by catalytic deoxygenation of the organic fraction of liquid products of pyrolysis of plant biomass has the following advantages compared to its analogue:

- use of a nitrogen-hydrogen mixture with a hydrogen content of 20±5 vol.% in the deoxygenation process;

- the use of a two-component deoxygenation catalyst containing one transition or noble metal selected from Pd, Ru, Ni, and a carrier - hyper-crosslinked polystyrene;

- reduction in deoxygenation temperature by 50-80°C;

- increase in the degree of deoxygenation by 11-30%;

- reduction of deoxygenation time by 1.5-3 hours due to the use of a supercritical solvent;

- reduction in the degree of catalyst deactivation by 3-5%;

- increase in the total selectivity for benzene and toluene with a total selectivity of 22-34%.

The inclusion of each of the stages in the method is mandatory and none of them can be excluded from the method, as well as changing their order and conditions for carrying out the stages, as this will lead to a significant decrease in the rate of deoxygenation of the organic fraction of the products of pyrolysis of plant biomass, the yield of benzene and toluene and the degree removing oxygen.

The deoxygenation catalyst is prepared by hydrothermal precipitation at a nitrogen pressure of 6.0 MPa, a temperature of 200°C with constant stirring at a speed of 500 rpm for 15 minutes. When preparing the catalyst, a carrier is used - hypercrosslinked polystyrene, a metal salt (Ni, Ru or Pd) and sodium bicarbonate. After completion of the synthesis, the resulting catalyst is filtered under vacuum and dried at 110°C for 12 hours. The method of preparing the catalyst is described in detail in the works (The influence of temperature and pressure on the structure of polymer catalysts synthesized in subcritical water / Markova M.E., Stepacheva A.A., Kosivtsov Yu.Yu., Sidorov A.I., Matveeva V.G. ., Sulman M.G. // Supercritical fluids: theory and practice. 2020. T. 15. No. 3. Hydrogen-free deoxygenation of bio-oil model compounds over sulfur-free polymer supported catalysts / Stepacheva A.A., Markova M.E., Lugovoy Yu.V., Chalov K.V., Sulman M.G., Matveeva V.G., Panfilov V.I., Sulman E.M. // Catalysis for Sustainable Energy 2020. T. 7. P. 29).

The use of a solvent selected from 2-propanol, ethanol, and supercritical methanol is necessary to ensure a high rate and degree of deoxygenation, as well as to reduce the degree of catalyst deactivation when it is reused. The use of propanol-2 solvent in a supercritical state provides additional hydrogen donation to reduce the consumption of hydrogen gas.

The use of a temperature in the range of 270 ± 5°C is necessary to ensure the transition of the solvent to a supercritical state, as well as to ensure the proper rate and extent of deoxygenation and selectivity to benzene and toluene. Reducing the temperature below 265°C leads to a decrease in the rate and extent of deoxygenation. An increase in temperature above 275°C leads to a decrease in selectivity to benzene and toluene.

The use of a nitrogen-hydrogen mixture with a hydrogen content of 20 ± 5 vol.% is necessary to ensure the proper rate and extent of deoxygenation and selectivity to benzene and toluene. Reducing the hydrogen content in the mixture below 15 vol.% leads to a decrease in the degree of deoxygenation. An increase in the hydrogen content in the mixture above 25 vol.% leads to a decrease in selectivity to benzene and toluene.

The use of an initial pressure of the nitrogen-hydrogen mixture of 1.5 ± 0.5 MPa is necessary to ensure the transition of the solvent to the supercritical state, as well as to ensure the proper rate and extent of deoxygenation and selectivity to benzene and toluene. Reducing the initial pressure below 1 MPa leads to a decrease in the degree of deoxygenation. An increase in the initial pressure of the nitrogen-hydrogen mixture above 2 MPa leads to a decrease in selectivity to benzene and toluene.

A pyrolysis products/catalyst ratio of 30 ± 5:1 (wt.) is necessary to ensure the proper rate and extent of deoxygenation and selectivity to benzene and toluene. A decrease in the ratio of pyrolysis products/catalyst below 25:1 (wt.) leads to a decrease in selectivity to benzene and toluene. Increasing the ratio of pyrolysis products/catalyst above 35:1 (wt.) leads to a decrease in the rate and degree of deoxygenation.

The use of a deoxygenation catalyst prepared by hydrothermal deposition method containing one metal selected from Ni, Ru or Pd, preferably Pd, with a content of 1±0.25 wt. %, and the carrier is hyper-crosslinked polystyrene containing 99±0.25 wt. %, is necessary to achieve the highest rate of substrate conversion and achieve the maximum yield of benzene and toluene.

Reducing the Pd content below 0.75 wt. % leads to a decrease in the degree of deoxygenation. Increasing the Pd content above 1.25 wt. % leads to a decrease in selectivity to benzene and toluene. Changing the catalyst synthesis method leads to a decrease in the rate and degree of deoxygenation (Conversion of bio-oil obtained from wood waste in a supercritical solvent / Dmitrieva A.A., Stepacheva A.A., Matveeva V.G. // Supercritical fluid technologies in solving environmental problems. Materials of the XIII All-Russian school-conference of young scientists named after V.V. Lunin. 44-48; Upgrading of liquid pyrolysis products in the presence of catalysts on a polymer carrier / Dmitrieva A.A., Stepacheva A.A. Matveeva V.G., Sulman M.G. // New catalytic processes of deep processing of hydrocarbon raw materials and biomass. Abstracts of the Fifth School of Young Scientists, Krasnoyarsk, 2021. pp. 24-25).

Reduction of the catalyst in a stream of hydrogen at 300±5°C for 3±0.5 hours is necessary to ensure proper catalyst activity. Reducing the catalyst reduction temperature below 295°C and reducing the reduction time to less than 2.5 hours leads to a decrease in the rate and degree of deoxygenation. An increase in the catalyst reduction temperature above 305°C leads to destruction of the polymer network of the support and loss of catalyst activity, which leads to a decrease in the rate and degree of deoxygenation. Increasing the catalyst recovery time above 3.5 hours is impractical, since it does not lead to an increase in the rate and degree of deoxygenation, as well as to an increase in selectivity to benzene and toluene.

Stirring the reaction mixture at a speed of 1200±100 rpm is necessary to ensure uniform distribution of the components of the reaction mixture in the volume of the reactor, and, consequently, to increase the speed of the deoxygenation process by reducing mass transfer restrictions. Reducing the stirring speed below 1100 rpm results in a decrease in the rate and extent of deoxygenation. Increasing the stirring speed above 1300 rpm is not advisable, since it does not affect the rate and degree of deoxygenation.

Stirring the reaction mixture for 60 ± 5 min is necessary to ensure a high degree of deoxygenation and high selectivity to benzene and toluene. Reducing the mixing time to less than 55 minutes leads to a decrease in the degree of deoxygenation. Increasing the stirring time above 65 min leads to a decrease in selectivity to benzene and toluene.

The method for producing benzene and toluene by catalytic deoxygenation of the organic fraction of liquid products of pyrolysis of plant biomass is disclosed in examples 1-57, the main parameters of the reaction according to examples 1-57 are given in table 1 and in table 2, which shows the results of deoxygenation of the organic fraction of liquid products of pyrolysis of pine sawdust ordinary according to examples 1-57.

Example 1

The deoxygenation catalyst (DT) is prepared by hydrothermal precipitation method. A suspension is prepared containing 1 g of carrier - hypercrosslinked polystyrene (HPC), 0.0211 g of palladium acetate, 0.1000 g of sodium bicarbonate in 15 ml of distilled water. The suspension is placed in a batch reactor cell equipped with a thermostat, a pressure and temperature sensor, and a four-blade stirrer. The reactor is sealed and purged with nitrogen three times to remove air. Then the nitrogen pressure is set to 6.0 MPa and the reactor is heated to 200°C with constant stirring at a speed of 500 rpm. After reaching the operating temperature, catalyst synthesis is carried out within 15 minutes. After completion of the synthesis, the mixture is cooled to room temperature and filtered under vacuum. The resulting catalyst is dried at 110°C for 12 hours.

Deoxygenation catalyst containing 1 wt. % Pd and 99 wt. % SPS prepared by hydrothermal deposition is preliminarily reduced in a stream of hydrogen at 300°C for 3 hours.

Take 1.5 g of the organic fraction of the liquid products of pyrolysis of Scots pine sawdust and dissolve it in 30 ml of solvent. Propanol-2 is used as a solvent. Take 0.05 g of catalyst and disperse it in the resulting solution. The ratio of pyrolysis products/catalyst is 30:1. The suspension is placed in a batch reactor cell equipped with a thermostat, a pressure and temperature sensor, and a magnetic stirrer. The reactor cell is sealed and purged three times with nitrogen to remove air. Then the nitrogen in the reactor is replaced with a mixture containing 20 vol.% hydrogen and 80 vol.% nitrogen under a pressure of 1.5 MPa and the reactor is heated to a temperature of 270°C with constant stirring at a speed of 1200 rpm. After reaching operating temperature, the deoxygenation process is carried out for 60 minutes. After the process is completed, the reaction mixture is cooled to room temperature and a sample of the liquid phase is taken for analysis.

The analysis of deoxygenation products is carried out by GC-MS using a gas chromatograph GC-2010 and a mass spectrometer GCMS-QP2010S (SHIMADZU, Japan) with a chromatographic column HP-1MS 30 m long, 0.25 mm in diameter and 0.25 μm film thickness.

The degree of deoxygenation (DOC) is determined according to the equation:

where Σn(HC) is the total amount of reaction products that do not contain oxygen;

Σn(PR) is the total amount of all reaction products.

Selectivity for benzene and toluene is determined according to the equation:

where n(BT) is the total amount of benzene and toluene in the deoxygenation products.

The rate of deoxygenation is determined according to the equation:

where Σn(HC) ₅₀ is the total amount of reaction products that do not contain oxygen at 50% conversion, mol;

n _cat - amount of catalyst metal, mol;

τ ₅₀ - time to achieve 50% conversion.

The loss of catalyst activity after 20 consecutive cycles is determined according to the equation:

where SDO ₁ is the degree of deoxygenation in the first cycle, %;

SDO ₂₀ - degree of deoxygenation in the 20th cycle, %.

Example 2

Similar to example 1, but methanol is used as a solvent.

Example 3

Similar to example 1, but ethanol is used as a solvent.

Example 4

Similar to example 1, however, a system containing 1 wt. is used as a catalyst. % Ru and 99 wt. % THX.

The deoxygenation catalyst is prepared by hydrothermal precipitation method. A suspension is prepared containing 1 g of carrier - hyper-cross-linked polystyrene, 0.0258 g of ruthenium hydroxotrichloride dihydrate, 0.1000 g of sodium bicarbonate in 15 ml of distilled water. The suspension is placed in a batch reactor cell equipped with a thermostat, a pressure and temperature sensor, and a four-blade stirrer. The reactor is sealed and purged with nitrogen three times to remove air. Then the nitrogen pressure is set to 6.0 MPa and the reactor is heated to 200°C with constant stirring at a speed of 500 rpm. After reaching the operating temperature, catalyst synthesis is carried out within 15 minutes. After completion of the synthesis, the mixture is cooled to room temperature and filtered under vacuum. The resulting catalyst is dried at 110°C for 12 hours.

Example 5

Similar to example 1, however, a system containing 1 wt. is used as a catalyst. % Ni and 99 wt. % THX.

The deoxygenation catalyst is prepared by hydrothermal precipitation method. Prepare a suspension containing 1 g of carrier - overcross-linked polystyrene, 0.0429 g of nickel acetate tetrahydrate, 0.1000 g of sodium bicarbonate in 15 ml of distilled water. The suspension is placed in a batch reactor cell equipped with a thermostat, a pressure and temperature sensor, and a four-blade stirrer. The reactor is sealed and purged with nitrogen three times to remove air. Then the nitrogen pressure is set to 6.0 MPa and the reactor is heated to 200°C with constant stirring at a speed of 500 rpm. After reaching the operating temperature, catalyst synthesis is carried out within 15 minutes. After completion of the synthesis, the mixture is cooled to room temperature and filtered under vacuum. The resulting catalyst is dried at 110°C for 12 hours.

Example 6

Similar to example 1, however, a system containing 1 wt. is used as a catalyst. % Pd and 99 wt. % THX.

The deoxygenation catalyst is prepared by impregnation method. A suspension containing 1 g of carrier - hypercrosslinked polystyrene, 0.0211 g of palladium acetate, 5 ml of tetrahydrofuran, 1 ml of methanol and 3 ml of distilled water, is stirred using a magnetic stirrer in air at room temperature for 10 minutes. After stirring, the suspension is dried at 75°C for 1 hour, then washed with 10 ml of distilled water and dried at 110°C for 12 hours.

Example 7

Similar to example 1, but the catalyst is not subjected to preliminary reduction.

Example 8

Similar to example 1, but the catalyst is restored at a temperature of 295°C.

Example 9

Similar to example 1, but the catalyst is restored at a temperature of 280°C.

Example 10

Similar to example 1, but the catalyst is restored at a temperature of 270°C.

Example 11

Similar to example 1, but the catalyst is restored at a temperature of 305°C.

Example 12

Similar to example 1, but the catalyst is restored at a temperature of 310°C.

Example 13

Similar to example 1, however, the catalyst is restored at a temperature of 320C.

Example 14

Similar to example 1, but the catalyst recovery is carried out for 1.5 hours.

Example 15

Similar to example 1, but the catalyst recovery is carried out for 2 hours.

Example 16

Similar to example 1, but the catalyst recovery is carried out for 2.5 hours.

Example 17

Similar to example 1, but the catalyst recovery is carried out for 3.5 hours.

Example 18

Similar to example 1, but the catalyst recovery is carried out for 4 hours.

Example 19

Similar to example 1, but the catalyst recovery is carried out for 4.5 hours.

Example 20

Similar to example 1, however, a system containing 0.75 wt. is used as a catalyst. % Pd and 99.25 wt. % THX. To prepare the catalyst, use a suspension containing 1 g of carrier - hypercrosslinked polystyrene, 0.0160 g of palladium acetate, 0.1000 g of sodium bicarbonate in 15 ml of distilled water.

Example 21

Similar to example 1, however, a system containing 0.5 wt. is used as a catalyst. % Pd and 99.5 wt. % THX. To prepare the catalyst, use a suspension containing 1 g of carrier - hypercrosslinked polystyrene, 0.0106 g of palladium acetate, 0.1000 g of sodium bicarbonate in 15 ml of distilled water.

Example 22

Similar to example 1, however, a system containing 1.25 wt. is used as a catalyst. % Pd and 98.75 wt. % THX. To prepare the catalyst, use a suspension containing 1 g of carrier - hypercrosslinked polystyrene, 0.0266 g of palladium acetate, 0.1000 g of sodium bicarbonate in 15 ml of distilled water.

Example 23

Similar to example 1, however, a system containing 1.5 wt. is used as a catalyst. % Pd and 98.5 wt. % THX. To prepare the catalyst, use a suspension containing 1 g of carrier - hypercrosslinked polystyrene, 0.0319 g of palladium acetate, 0.1000 g of sodium bicarbonate in 15 ml of distilled water.

Example 24

Similar to example 1, however, a system containing 2 wt. is used as a catalyst. % Pd and 98 wt. % THX. To prepare the catalyst, use a suspension containing 1 g of carrier - hypercrosslinked polystyrene, 0.0426 g of palladium acetate, 0.1000 g of sodium bicarbonate in 15 ml of distilled water.

Example 25

Similar to example 1, but the stirring speed is 1000 rpm.

Example 26

Similar to example 1, but the mixing speed is 1100 rpm.

Example 27

Similar to example 1, but the mixing speed is 1300 rpm.

Example 28

Similar to example 1, but the mixing speed is 1400 rpm.

Example 29

Similar to example 1, but the mixing speed is 1500 rpm.

Example 30

Similar to example 1, but the deoxygenation process is carried out at a temperature of 250°C.

Example 31

Similar to example 1, however, the deoxygenation process is carried out at a temperature of 260°C.

Example 32

Similar to example 1, however, the deoxygenation process is carried out at a temperature of 265°C.

Example 33

Similar to example 1, however, the deoxygenation process is carried out at a temperature of 275°C.

Example 34

Similar to example 1, however, the deoxygenation process is carried out at a temperature of 280°C.

Example 35.

Similar to example 1, however, the deoxygenation process is carried out at a temperature of 290°C.

Example 36

Similar to example 1, but the deoxygenation process is carried out at a temperature of 300°C.

Example 37

Similar to example 1, however, the deoxygenation process is carried out at an initial pressure of a mixture containing 20 vol.% hydrogen and 80 vol.% nitrogen, 0.5 MPa.

Example 38

Similar to example 1, however, the deoxygenation process is carried out at an initial pressure of a mixture containing 20 vol.% hydrogen and 80 vol.% nitrogen, 1.0 MPa.

Example 39

Similar to example 1, however, the deoxygenation process is carried out at an initial pressure of a mixture containing 20 vol.% hydrogen and 80 vol.% nitrogen, 2.0 MPa.

Example 40

Similar to example 1, however, the deoxygenation process is carried out at an initial pressure of a mixture containing 20 vol.% hydrogen and 80 vol.% nitrogen, 2.5 MPa.

Example 41

Similar to example 1, however, the deoxygenation process is carried out at an initial pressure of a mixture containing 20 vol.% hydrogen and 80 vol.% nitrogen, 3.0 MPa.

Example 42

Similar to example 1, however, the deoxygenation process is carried out using a mixture containing 10 vol.% hydrogen and 90 vol.% nitrogen.

Example 43

Similar to example 1, however, the deoxygenation process is carried out using a mixture containing 15 vol.% hydrogen and 85 vol.% nitrogen.

Example 44

Similar to example 1, however, the deoxygenation process is carried out using a mixture containing 25 vol.% hydrogen and 75 vol.% nitrogen.

Example 45

Similar to example 1, however, the deoxygenation process is carried out using a mixture containing 30 vol.% hydrogen and 70 vol.% nitrogen.

Example 46

Similar to example 1, however, the deoxygenation process is carried out using a mixture containing 40 vol.% hydrogen and 60 vol.% nitrogen.

Example 47

Similar to example 1, however, the deoxygenation process is carried out using a mixture containing 50 vol.% hydrogen and 50 vol.% nitrogen.

Example 48

Similar to example 1, however, the deoxygenation process is carried out using 0.15 g of catalyst. The ratio of pyrolysis products/catalyst in this case is 10:1 wt. parts.

Example 49

Similar to example 1, however, the deoxygenation process is carried out using 0.075 g of catalyst. The ratio of pyrolysis products/catalyst is 20:1 wt. parts.

Example 50

Similar to example 1, however, the deoxygenation process is carried out using 0.06 g of catalyst. The ratio of pyrolysis products/catalyst is 25:1 wt. parts.

Example 51

Similar to example 1, however, the deoxygenation process is carried out using 0.0429 g of catalyst. The ratio of pyrolysis products/catalyst is 35:1 wt. parts.

Example 52

Similar to example 1, however, the deoxygenation process is carried out using 0.0375 g of catalyst. The ratio of pyrolysis products/catalyst is 40:1 wt. parts.

Example 53

Similar to example 1, however, the deoxygenation process is carried out using 0.03 g of catalyst. The ratio of pyrolysis products/catalyst in this case is 50:1 wt. parts.

Example 54

Similar to example 1, but the process is carried out for 50 minutes.

Example 55

Similar to example 1, but the process is carried out for 55 minutes.

Example 56

Similar to example 1, but the process is carried out for 65 minutes.

Example 57

Similar to example 1, but the process is carried out for 70 minutes.

The extent of deoxygenation, rate of deoxygenation, selectivity to benzene and toluene, and loss of deoxygenation catalyst activity after 20 consecutive cycles obtained in accordance with Examples 1-57 are presented in Table 2.

As can be seen from Table 1 and Table 2, the maximum degree of deoxygenation and selectivity to benzene and toluene, according to examples 1.4-6, 20-24, are observed when using a catalytic system containing 1±0.25 wt. % Pd and 99±0.25 wt. % ATP prepared by hydrothermal precipitation, which allows us to recommend this catalyst for the production of benzene and toluene by catalytic deoxygenation of the organic fraction of liquid products of pyrolysis of plant biomass.

As can be seen from Table 1 and Table 2, the maximum degree of deoxygenation and selectivity to benzene and toluene, according to examples 7-19, are observed when restoring a catalytic system containing 1 wt. % Pd and 99 wt. % ATP, at 300±5°C for 3±0.5 hours, which makes it possible to recommend these catalyst recovery parameters for the production of benzene and toluene by catalytic deoxygenation of the organic fraction of liquid products of pyrolysis of plant biomass.

As can be seen from Table 1 and Table 2, the maximum degree of deoxygenation and selectivity to benzene and toluene, according to examples 1-3, 25-29, 54-57, are observed when the process is carried out in propanol-2 for 60±5 minutes with stirring speed 1200±100 rpm, which allows us to recommend these parameters for the production of benzene and toluene by catalytic deoxygenation of the organic fraction of liquid products of pyrolysis of plant biomass.

As can be seen from Table 1 and Table 2, the maximum degree of deoxygenation and selectivity to benzene and toluene, according to examples 30-41, are observed when the process is carried out at a temperature of 270±5°C and the initial pressure of a mixture containing 20 vol.% hydrogen and 80 vol. .% nitrogen, 1.5±0.5 MPa, which allows us to recommend these parameters for the production of benzene and toluene by catalytic deoxygenation of the organic fraction of liquid products of pyrolysis of plant biomass.

As can be seen from Table 1 and Table 2, the maximum degree of deoxygenation and selectivity to benzene and toluene, according to examples 42-53, are observed when the process is carried out in an atmosphere of a mixture of gases containing 20±5 vol.% hydrogen and 80±5 vol.% nitrogen , using a ratio of pyrolysis products: catalyst equal to 30±5:1, which allows us to recommend these parameters for the production of benzene and toluene by catalytic deoxygenation of the organic fraction of liquid products of pyrolysis of plant biomass.

From the results given in Table 1 and Table 2, we can conclude that the use of a supercritical solvent in the process of deoxygenation of pyrolysis products of plant raw materials significantly increases the degree of deoxygenation, increases the speed of the process and selectivity with respect to the target products (benzene and toluene) , and also reduces the loss of deoxygenation catalyst activity

The proposed method for producing benzene and toluene by catalytic deoxygenation of the organic fraction of liquid products of pyrolysis of plant biomass using a deoxygenation catalyst prepared by hydrothermal deposition containing a transition or noble metal selected from Ni, Ru and Pd and a carrier (hyper-cross-linked polystyrene) is a promising opportunity to intensify the process deoxygenation.

Claims (3)

1. A method for producing benzene and toluene by catalytic deoxygenation of the organic fraction of liquid products of pyrolysis of plant biomass, including one-stage processing in an autoclave reactor at a pressure of 1.5 ± 0.5 MPa, temperature 270 ± 5 ° C, using a catalyst containing transition metal oxides , characterized in that it additionally includes the use of a solvent selected from 2-propanol, ethanol, methanol, in a supercritical state, the use of a deoxygenation catalyst prepared by hydrothermal precipitation containing 1±0.25 wt. % transition or noble metal selected from Ni, Ru and Pd, and 99 ± 0.25 wt. % of carrier, hyper-crosslinked polystyrene, in the deoxygenation process a nitrogen-hydrogen mixture with a hydrogen content of 20±5 vol.% is used, the process is carried out for 60±5 minutes with stirring at a speed of 1200±100 rpm, while the amount of catalyst is 0. 06-0.429 g, the ratio of pyrolysis products/catalyst is 30±5:1 wt. parts, the deoxygenation catalyst is reduced for 3±0.5 hours at a temperature of 300±5°C. 2. A method for producing benzene and toluene by catalytic deoxygenation of the organic fraction of liquid products of pyrolysis of plant biomass according to claim 1, characterized in that propanol-2 is used as a solvent. 3. A method for producing benzene and toluene by catalytic deoxygenation of the organic fraction of liquid products of pyrolysis of plant biomass according to claim 1, characterized in that Pd is used as a transition or noble metal in the deoxygenation catalyst.