Method for synergistically producing light oil product through catalytic hydrogenation of biomass and heavy oil

Abstract

The invention belongs to the technical field of synergistic conversion and utilization of biomass and fossil resources, and particularly relates to a method for synergistically producing a light oil product through catalytic hydrogenation of biomass and heavy oil. Biomass and heavy oil are subjected to ozone oxidation pretreatment, and after treatment, light oil products are produced through co-catalytic hydrogenation synergistic conversion; wherein the mass ratio of the biomass to the heavy oil is (1: 100)-(30: 100). The ozone oxidation treatment conditions are mild, the operation is convenient, the treatment time is short, and the treatment efficiency is greatly improved; the catalytic hydrogenation synergistic conversion efficiency of the biomass and the heavy oil is efficiently promoted, the economic benefits of oil refining enterprises are favorably improved, the high-value utilization of biomass resources is enhanced, and the national government policy of carbon emission reduction is assisted.

Description

Technical Field

[0001] The present invention belongs to the technical field of coordinated conversion and utilization of biomass and fossil resources, and specifically relates to a method for coordinated production of light oil products by catalytic hydrogenation of biomass and heavy oil. Background Art

[0002] Due to long-term exploitation, the world's oil resources are becoming heavier and inferior. Statistics show that the reserves of heavy crude oil account for about 50% of the world's recoverable crude oil. Due to the difficulty in processing heavy and inferior oil and high energy consumption, the economic benefits of oil refining companies are generally low, so the efficient processing and utilization of heavy and inferior oil is an important problem that needs to be solved urgently. It is worth noting that biomass resources such as straw and trees produced in the process of agricultural and forestry production are very important carbon-containing renewable resources. The global annual output is as high as tens of billions of tons, which is an important source of potential sustainable energy. However, most of these agricultural and forestry wastes are discarded or incinerated, causing serious environmental damage and waste of resources. Therefore, it is of great significance to carry out high-value utilization of these agricultural and forestry waste biomass resources. Patent 202111652700.5 discloses a technology for the synergistic conversion of heavy oil and lignin resources. This process organically combines the two reactions of direct liquefaction of lignin and hydrocracking of heavy oil. The heavy oil in the system is both a reactant and a solvent to promote the dissolution of lignin under high temperature and high pressure, while providing a place for storage and transfer of hydrogen. At the same time, the raw material lignin has a high oxygen content, and the reaction system will produce a certain amount of water during the hydrogenation process, which will promote the dissolution and removal of metal impurities in the heavy oil and the cracking of heavy oil molecules under high temperature and high pressure. This solves the problems of low oil yield and easy coking of the device in the existing lignin processing process. This technology is of great significance for the technological upgrading of oil refining enterprises, improving the utilization rate of renewable resources and reducing carbon dioxide emissions. Patent 202210690797.7 discloses a method for synthesizing an oil-soluble catalyst for the synergistic conversion of biomass resources and heavy oil. The catalyst is composed of transition metal ions and organic ligands, and is evenly dispersed in the low-quality heavy oil and biomass reaction system. During the reaction, metal sulfide particles with high activity are generated in situ to participate in the reaction. The catalyst has high activity and can promote the generation of hydrogen radicals and the reaction of hydrogenated aromatics. More importantly, it can inhibit dehydrogenation and condensation, and promote the cracking, hydrogenation and isomerization reactions of polymer compounds. However, due to the complex molecular structure of biomass and heavy oil, and the high content of impurity elements, the catalytic hydrogenation synergistic conversion technology of biomass and heavy oil still has many shortcomings in terms of light oil yield and coking rate, and needs further optimization and improvement. Summary of the invention

[0003] In view of the shortcomings of the existing technology for the catalytic hydrogenation synergistic conversion of biomass and heavy oil, the purpose of the present invention is to disclose a method for the catalytic hydrogenation synergistic production of light oil products by biomass and heavy oil.

[0004] To achieve the above object, the technical solution adopted by the present invention is:

[0005] A method for synergistically producing light oil products by catalytic hydrogenation of biomass and heavy oil, wherein the biomass and heavy oil are pretreated by ozone oxidation, and then synergistically converted by co-catalytic hydrogenation to produce light oil products; wherein the mass ratio of biomass to heavy oil is 1:100 to 30:100.

[0006] The biomass and heavy oil are mixed and shaken with a solvent, and then ozone is introduced to treat the shaken substances; wherein the ozone treatment is carried out for 0.5 to 4 hours with a concentration of 50-200 mg / L.

[0007] The ozone introduction rate is 10-40mL / min.

[0008] The solvent is one or more of water, methanol, ethanol, acetone, acetic acid, and oxalic acid; the mass ratio of the added solvent to the biomass particles is 1:1 to 1:100.

[0009] When two or more solvents are selected, they can be mixed in any mass ratio;

[0010] Furthermore, when the solvent is a mixture of water and an organic solvent, the mass ratio of water to the organic solvent is 1:1-1:10; when the solvent is a mixture of an organic solvent and an organic solvent, the two are mixed in any mass ratio.

[0011] The oscillation is ultrasonic oscillation with an ultrasonic frequency of 20 to 50 kHz and a treatment time of 0.5 to 3 hours.

[0012] Further,

[0013] (1) crushing and screening the biomass raw material to obtain particles of 10 to 100 mesh, and then mixing with heavy oil in an autoclave;

[0014] (2) adding a solvent to the biomass and heavy oil mixture obtained in step (1), followed by shaking;

[0015] (3) introducing ozone into the mixed solution after the oscillation treatment in step (2) for pretreatment;

[0016] (4) adding an oil-soluble catalyst required for co-catalytic hydrogenation to the mixed solution obtained in step (3);

[0017] (5) hydrogen is introduced into the autoclave of step (4) to replace the air in the autoclave, and then a hydrogenation reaction is carried out in the presence of hydrogen to obtain a light component oil product.

[0018] The biomass in step (1) is one or more of wheat straw, corn straw, soybean straw, peanut straw or poplar, birch, and pine, and the heavy oil is one or more of heavy crude oil, atmospheric residue oil, vacuum residue oil, catalytic cracking slurry, hydrocracking tail oil, deasphalted oil, coking heavy oil, and shale oil.

[0019] The oil-soluble catalyst in step (4) is composed of transition metal ions and organic acid ligands; wherein the metal element is one or more of Fe, Co, Mo, Ni, and W, and the organic acid is one or a mixture of cyclohexane acid, isooctanoic acid, or tartaric acid; and the amount of the oil-soluble catalyst added is 20 to 500 ppm.

[0020] The catalyst is prepared with the above ingredients according to the description in the application with patent number 202210690797.7.

[0021] In the step (5), the hydrogenation reaction pressure is 5 to 15 MPa, the reaction temperature is 300 to 450° C., and the reaction time is 2 to 10 hours.

[0022] The advantages of the present invention are:

[0023] 1. The present invention utilizes ozone to pretreat biomass and heavy oil, initially breaking the internal connecting bonds of biomass and heavy oil molecules, increasing the mutual solubility of biomass and heavy oil, improving the yield of light oil products, and reducing the reaction coking rate.

[0024] 2. The present invention utilizes ultrasonic oscillation to pretreat biomass and heavy oil raw materials, which is beneficial to increase the penetration of solvents and ozone, and is beneficial to breaking the internal connecting bonds of biomass and heavy oil molecules.

[0025] 3. The ozone oxidation treatment conditions of the present invention are mild, easy to operate, and the treatment time is short, which greatly improves the treatment efficiency.

[0026] 4. The ozone oxidation pretreatment process proposed in the present invention can effectively promote the synergistic conversion efficiency of biomass and heavy oil catalytic hydrogenation, help improve the economic benefits of oil refining enterprises, strengthen the high-value utilization of biomass resources, and assist the national policy of carbon emission reduction. DETAILED DESCRIPTION

[0027] The present invention is further explained below in conjunction with specific embodiments, but the present invention is not limited to the following embodiments.

[0028] The present invention utilizes the strong oxidizing property of ozone to initially break the connecting bonds inside the biomass and heavy oil molecules, increase the mutual solubility of biomass and heavy oil, improve the efficiency of the catalytic hydrogenation synergistic conversion of biomass and heavy oil, increase the yield of light oil products, and reduce the reaction coking rate. The ozone oxidation treatment conditions of the present invention are mild, easy to operate, and have a short processing time, which greatly improves the processing efficiency; it effectively promotes the efficiency of the catalytic hydrogenation synergistic conversion of biomass and heavy oil, helps to improve the economic benefits of oil refining enterprises, strengthens the high-value utilization of biomass resources, and helps the national policy of carbon emission reduction.

[0029] The catalyst used in the following examples can be prepared as described in application number 202210690797.7.

[0030] When the solvent is a mixture of water and an organic solvent, the mass ratio of water to the organic solvent is 1:1-1:10; when the solvent is a mixture of an organic solvent and an organic solvent, the two are mixed in any mass ratio.

[0031] The following examples take the atmospheric residue oil of Shengli Oilfield (four-component analysis data are shown in Table 1) as an example of heavy oil, pre-treated with biomass, and then co-catalyzed and hydrogenated to produce light oil products.

[0032] Table 1. Properties of Shengli Oilfield atmospheric residue raw materials

[0033] Four component types Mass fraction (wt%) Saturation 12 Aroma 36 Gel 23 C7-Asphaltene 29

[0034] Embodiment 1:

[0035] 10g of poplar wood chips with a particle size of 20-40 mesh and 50g of heavy oil were loaded into a high-pressure reactor, and then 2g of liquid A consisting of water and acetic acid (the mass ratio of the two was 1:1) was added to the reactor; then the obtained mixed solution was subjected to ultrasonic oscillation treatment, the ultrasonic oscillation frequency was 30kHz, and the treatment time was 1h. Then, ozone with a concentration of 100mg / L was introduced into the above mixed solution for 1h (the introduction rate of ozone was 20mL / min). After the treatment was completed, 30ppm of nickel isooctanoate catalyst was added to the reactor, hydrogen was filled and replaced three times to exclude the air in the reactor, and then 8MPa of hydrogen was filled, and the reaction was carried out at 380℃ and 600r speed for 6h. Finally, the liquid product was filtered and separated, the coking rate was 12%, and the oil yield reached 88%. The four-component separation results of the obtained oil are shown in Table 2.

[0036] Embodiment 2:

[0037] 5g of pine sawdust with a particle size of 40-60 mesh and 50g of heavy oil were loaded into a high-pressure reactor, and then 5g of liquid A consisting of ethanol and acetic acid (the mass ratio of the two was 1:1) was added to the reactor; then the resulting mixed solution was subjected to ultrasonic oscillation treatment, the ultrasonic oscillation frequency was 30kHz, and the treatment time was 2h. Then, 180mg / L ozone was introduced into the above-mentioned mixed solution for 2h (the introduction rate of ozone was 25mL / min). After the treatment was completed, 50ppm of nickel isooctanoate and cobalt isooctanoate catalysts were added to the reactor, hydrogen was filled and replaced three times to exclude the air in the reactor, and then 10MPa of hydrogen was filled, and the reaction was carried out at 400℃ and 600r speed for 4h. Finally, the liquid product was filtered and separated, the coking rate was 5%, and the oil yield reached 95%. The four-component separation results of the obtained oil products are shown in Table 2.

[0038] Embodiment 3:

[0039] 10g of wheat straw with a particle size of 40-60 mesh and 50g of heavy oil were loaded into a high-pressure reactor, and then 1g of liquid A composed of acetone and oxalic acid (the mass ratio of the two was 1:2) was added to the reactor; then the resulting mixed solution was subjected to ultrasonic oscillation treatment, the ultrasonic oscillation frequency was 20kHz, and the treatment time was 1h. Then, ozone with a concentration of 100mg / L was introduced into the above mixed solution for 2h (the introduction rate of ozone was 20mL / min). After the treatment was completed, 20ppm of nickel cyclohexane acid catalyst was added to the reactor, hydrogen was filled and replaced three times to exclude the air in the reactor, and then 12MPa of hydrogen was filled, and the reaction was carried out at 360℃ and 600r speed for 3h. Finally, the liquid product was filtered and separated, the coking rate was 6%, and the oil yield reached 94%. The four-component separation results of the obtained oil are shown in Table 2.

[0040] Embodiment 4:

[0041] 5g of soybean straw with a particle size of 40-60 mesh and 50g of heavy oil were loaded into a high-pressure reactor, and then 5g of liquid A consisting of methanol and acetic acid (the mass ratio of the two was 2:1) was added to the reactor; then the obtained mixed solution was subjected to ultrasonic oscillation treatment, the ultrasonic oscillation frequency was 30kHz, and the treatment time was 2h. Then, ozone with a concentration of 180mg / L was introduced into the above mixed solution for 2h (the introduction rate of ozone was 25mL / min). After the treatment was completed, 50ppm of cyclopentane nickel-molybdenum catalyst with a nickel-molybdenum atomic ratio of 1:1 was added to the reactor, hydrogen was filled and replaced three times to exclude the air in the reactor, and then 10MPa of hydrogen was filled, and the reaction was carried out at 400℃ and 600r speed for 4h. Finally, the liquid product was filtered and separated, the coking rate was 8%, and the oil yield reached 92%. The four-component separation results of the obtained oil are shown in Table 2.

[0042] Embodiment 5:

[0043] 10g of birch sawdust with a particle size of 10-20 mesh and 50g of heavy oil were loaded into a high-pressure reactor, and then 1g of liquid A consisting of water and oxalic acid (the mass ratio of the two was 1:5) was added to the reactor; then the resulting mixed solution was subjected to ultrasonic oscillation treatment, the ultrasonic oscillation frequency was 30kHz, and the treatment time was 2h. Then, ozone with a concentration of 100mg / L was introduced into the above-mentioned mixed solution for 1h (the introduction rate of ozone was 20mL / min). After the treatment was completed, 100ppm of molybdenum isooctanoate catalyst was added to the reactor, hydrogen was filled and replaced three times to exclude the air in the reactor, and then 10MPa of hydrogen was filled, and the reaction was carried out for 3h at 430℃ and 600r speed. Finally, the liquid product was filtered and separated, the coking rate was 10%, and the oil yield reached 90%. The four-component separation results of the obtained oil products are shown in Table 2.

[0044] Comparative Example 1

[0045] 5g of pine sawdust with a particle size of 40-60 mesh and 50g of heavy oil were loaded into a high-pressure reactor, 50ppm of nickel octanoate and cobalt octanoate catalysts were added to the reactor, hydrogen was filled and replaced three times to remove the air in the reactor, and then 10MPa of hydrogen was filled, and the reaction was carried out for 4h at 400℃ and 600r. Finally, the liquid product was filtered and separated, the coking rate was 14%, and the oil yield reached 86%. The four-component separation results of the obtained oil are shown in Table 2.

[0046] Table 2. Separation results of four components of oil products

[0047]

Claims

1. A method for producing light oil products by catalytic hydrogenation of biomass and heavy oil, characterized in that: The biomass and heavy oil are pretreated by ozone oxidation, and then transformed by co-catalytic hydrogenation to produce light oil products; wherein the mass ratio of biomass to heavy oil is 1:100 to 30:

100.

2. The method for producing light oil products by catalytic hydrogenation of biomass and heavy oil according to claim 1, characterized in that: The biomass and heavy oil are mixed and shaken with a solvent, and then ozone is introduced to treat the shaken substances; wherein the ozone treatment is carried out for 0.5 to 4 hours with a concentration of 50-200 mg / L.

3. The method for producing light oil products by catalytic hydrogenation of biomass and heavy oil according to claim 2, characterized in that: The solvent is one or more of water, methanol, ethanol, acetone, acetic acid, and oxalic acid; the mass ratio of the added solvent to the biomass particles is 1:1 to 1:

100.

4. The method for producing light oil products by catalytic hydrogenation of biomass and heavy oil according to claim 2, characterized in that: The oscillation is ultrasonic oscillation with an ultrasonic frequency of 20 to 50 kHz and a treatment time of 0.5 to 3 hours.

5. The method for producing light oil products by catalytic hydrogenation of biomass and heavy oil according to any one of claims 1 to 4, characterized in that: (1) crushing and screening the biomass raw material to obtain particles of 10 to 100 mesh, and then mixing with heavy oil in an autoclave; (2) adding a solvent to the biomass and heavy oil mixture obtained in step (1), followed by shaking; (3) introducing ozone into the mixed solution after the oscillation treatment in step (2) for pretreatment; (4) adding an oil-soluble catalyst required for co-catalytic hydrogenation to the mixed solution obtained in step (3); (5) hydrogen is introduced into the autoclave of step (4) to replace the air in the autoclave, and then a hydrogenation reaction is carried out in the presence of hydrogen to obtain a light component oil product.

6. The method for producing light oil products by catalytic hydrogenation of biomass and heavy oil according to claim 5, characterized in that: The biomass in step (1) is one or more of wheat straw, corn straw, soybean straw, peanut straw or poplar, birch, and pine, and the heavy oil is one or more of heavy crude oil, atmospheric residue oil, vacuum residue oil, catalytic cracking slurry, hydrocracking tail oil, deasphalted oil, coking heavy oil, and shale oil.

7. The method for producing light oil products by catalytic hydrogenation of biomass and heavy oil according to claim 6, characterized in that: The oil-soluble catalyst in step (4) is composed of transition metal ions and organic acid ligands; wherein the metal element is one or more of Fe, Co, Mo, Ni, and W, and the organic acid is one or a mixture of cyclohexane acid, isooctanoic acid, or tartaric acid; and the amount of the oil-soluble catalyst added is 20 to 500 ppm.

8. The method for producing light oil products by catalytic hydrogenation of biomass and heavy oil according to claim 6, characterized in that: In the step (5), the hydrogenation reaction pressure is 5 to 15 MPa, the reaction temperature is 300 to 450° C., and the reaction time is 2 to 10 hours.

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