CN105733821B - Method for producing special oil product by rosin hydrogenation - Google Patents
Method for producing special oil product by rosin hydrogenation Download PDFInfo
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Abstract
The invention relates to a method for producing a special oil product by rosin hydrogenation, which comprises the steps of mixing rosin and a solvent, filtering the mixture to serve as a raw material, allowing the raw material and hydrogen to enter a hydrotreating reaction zone for reaction, performing gas-liquid separation on the obtained reaction effluent to obtain gas and liquid effluent, and dehydrating the obtained gas and then feeding the gas to a circulating hydrogen system; and mixing the obtained liquid effluent with hydrogen, then feeding the mixture into a hydro-upgrading reaction zone for hydro-upgrading reaction, and separating the hydro-upgrading reaction product to obtain low-aromatic solvent oil and transformer oil. The method provides a processing method for improving the economical efficiency of the rosin with lower added value, and develops a new raw material for the transformer oil.
Description
Technical Field
The invention relates to a rosin treatment method, in particular to a process method for producing special oil products by taking rosin as a raw material through hydrogenation.
Background
Rosin is a natural resin which is extremely rich in nature, does not contain impurities such as sulfur, nitrogen and the like, and is derived from renewable pine forest resources. China is a large country for producing rosin, the annual output of gum rosin is more than 60 million tons, which is the top of the world, and the output of rosin is increased continuously with the increase of the area of available gum rosin forest in China. In 2010, the annual output of rosin exceeds 80 ten thousand tons, while the deep processing utilization rate of rosin in China is only 35%, mainly export gum rosin is used, so that huge waste of rosin resources in China is caused, and the rosin deep processing products are urgently needed to be developed to improve the additional value of rosin. The main component of rosin is abietic acid type resin acid (molecular formula is C) 19 H 29 COOH) and most are monocarboxylic acids having a tricyclic phenanthrene skeleton and two double bonds, and rosin has disadvantages of being easily oxidized, brittle, and poor in thermal stability due to the double bonds and carboxyl groups, thereby limiting further industrial use thereofIs widely applied.
CN 201110024754.7 discloses a production method of water-white hydrogenated rosin, which comprises the steps of taking light-colored refined rosin obtained by purifying rosin as a hydrogenation raw material, preparing a solution by using a solvent, carrying out catalytic hydrogenation, and then separating the solvent by distillation to obtain the water-white hydrogenated rosin. Compared with the water white hydrogenated rosin produced by the traditional method, the water white hydrogenated rosin with low iodine value and low abietic acid has lighter color, higher hydrogenation degree, better stability and lower cost. However, this method has problems of low yield, poor continuity and low utilization rate.
CN201010578625.8 discloses a method for preparing colorless hydrogenated rosin ester resin, which comprises using distilled and purified rosin and esterified rosin ester as raw materials, catalytically hydrogenating under the action of solvent and high-efficiency catalyst, and distilling to separate solvent to obtain colorless hydrogenated rosin ester resin. The method for preparing the colorless hydrogenated rosin ester resin is simple and easy to implement, but has the problems of low purity and limited resources.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for producing special oil products by using rosin as a raw material through a combined process of hydrotreating-hydro-upgrading.
The invention provides a method for producing a special oil product by rosin hydrogenation, which comprises the following steps:
(1) Mixing rosin and a solvent at 130-160 ℃, filtering the mixture to be used as a raw material, feeding the raw material and hydrogen into a hydrotreating reaction zone in a gas-liquid countercurrent mode for reaction, and sequentially arranging a hydrofining catalyst and a hydro-upgrading catalyst A in the hydrotreating reaction zone according to a liquid phase flow direction;
(2) Carrying out gas-liquid separation on the reaction effluent obtained in the step (1) to obtain gas and liquid effluent, and dehydrating the obtained gas and then sending the gas to a circulating hydrogen system;
(3) And (3) mixing the liquid effluent obtained in the step (2) with hydrogen, then feeding the mixture into a hydro-upgrading reaction zone for hydro-upgrading reaction, wherein a hydro-upgrading catalyst B containing amorphous silica-alumina and modified Y zeolite is used in the hydro-upgrading reaction zone, and the hydro-upgrading reaction product is separated to obtain low-aromatic solvent oil and transformer oil.
In the method, the solvent in the step (1) can be one or more of low aromatic solvent oil, F-T synthetic light distillate, straight-run diesel oil and hydrocracking diesel oil, and preferably low aromatic solvent oil. The mass ratio of the rosin to the solvent is 1:1 to 1:5, preferably 1:2 to 1:3.
in the method of the invention, the rosin in the step (1) can be resin or turpentine.
In the method of the present invention, in the step (1), the loading volume ratio of the hydrogenation refining catalyst to the hydrogenation upgrading catalyst A in the hydrotreating reaction zone is 20: 80-80: 20, preferably 50: 50-80: 20.
in the method, the hydrofining catalyst used in the hydrotreating reaction zone can be selected from common commercial catalysts in the field, and can also be prepared according to general knowledge in the field. The commercial catalysts can be selected, such as 3936, 3996, FF-16, FF-26 and other hydrofining catalysts developed and produced by the Fushu petrochemical research institute (FRIPP).
In the process of the present invention, a hydro-upgrading catalyst A comprising amorphous silica-alumina and a modified Y zeolite is used in the hydrotreating reaction zone. The hydro-upgrading catalyst A comprises: 10 to 35 weight percent of amorphous silica-alumina, 2 to 15 weight percent of modified Y zeolite, 20 to 50 weight percent of VIB group metal (calculated by oxide) and 8 to 15 weight percent of VIII group metal (calculated by oxide). The properties of the amorphous silica-alumina used therein were as follows: contains 20-70 wt% of silicon oxide and has a specific surface area of 350-600 m 2 The pore volume is 1.0-2.0 mL/g, the infrared acidity is 0.20-0.40 mmol/g, the pore volume with the pore diameter of 4-10 nm accounts for 85-95 percent of the total pore volume,>the pore volume of 15nm accounts for less than 5% of the total pore volume; preferred properties are as follows: contains 25wt% -40 wt% of silicon oxide and has a specific surface area of 500-630 m 2 The pore volume is 1.2-1.6 mL/g. The properties of the modified Y zeolite used therein are as follows: siO 2 2 /Al 2 O 3 The molar ratio is 40-60, the unit cell constant is 2.420-2.450 nm, the relative crystallinity is 85% -95%, the infrared acidity is 0.2-0.4 mmol/g, wherein the medium and strong acids at 300-500 ℃ are distributed and concentrated, accounting for 60-70% of the total acid, and the specific surface areaIs 500-1000 m 2 The pore volume is 0.35-0.55 mL/g, wherein the pore volume of the secondary mesopores with the diameter of 4-15 nm accounts for 35-55% of the total pore volume. The specific surface area of the hydrogenation modified catalyst is 220-300 m 2 The pore volume is 0.3-0.5 mL/g, the pore volume with the pore diameter of 3-10 nm accounts for 80-95 percent of the total pore volume, preferably 85-95 percent, and the infrared acidity is 0.2-0.4 mmol/g.
In the method, a high-activity hydrogenation modification catalyst B containing amorphous silica-alumina and modified Y zeolite is used in the hydrogenation modification reaction zone. The hydro-upgrading catalyst comprises: 20 to 60 weight percent of amorphous silica-alumina, 5 to 25 weight percent of modified Y zeolite, 10 to 30 weight percent of VIB group metal (calculated by oxide) and 4 to 10 weight percent of VIII group metal (calculated by oxide). The properties of the amorphous silica-alumina used therein were as follows: 10wt% -60 wt% of silicon oxide, and the specific surface area is 400-650 m 2 Per gram, the pore volume is 1.0-1.8 mL/g, the infrared acidity is 0.34-0.50 mmol/g, the pore volume with the pore diameter of 4-10 nm accounts for 85-95 percent of the total pore volume,>the pore volume of 15nm accounts for less than 5% of the total pore volume; preferred properties are as follows: 10wt% -35 wt% of silicon oxide, and the specific surface is 530-650 m 2 The pore volume is 1.2-1.5 mL/g. The properties of the modified Y zeolite used therein were as follows: siO 2 2 /Al 2 O 3 The molar ratio is 40-60, the unit cell constant is 2.425-2.440 nm, the relative crystallinity is 80-100%, the infrared acidity is 0.1-0.5 mmol/g, wherein the medium and strong acid at 250-550 ℃ are distributed and concentrated, accounting for 60-70% of the total acid, and the specific surface area is 600-900 m 2 The pore volume is 0.3-0.6 mL/g, wherein the pore volume of the secondary mesopores with the diameter of 4-15 nm accounts for 40-50% of the total pore volume. The hydro-upgrading catalyst may further contain alumina, zirconia, titania and other components. The specific surface area of the hydrogenation modified catalyst is 220-300 m 2 The pore volume is 0.3-0.6 mL/g, the pore volume with the pore diameter of 3-10 nm accounts for 75-95 percent of the total pore volume, preferably 85-95 percent, and the infrared acidity is 0.3-0.5 mmol/g.
In the method, compared with the composition of the hydrogenation modification catalyst B, the total content of the VIB group metal and the VIII group metal in the hydrogenation modification catalyst B is 10-25 percent higher than that of the hydrogenation modification catalyst A, and the total content of the amorphous silica-alumina and the modified Y zeolite in the hydrogenation modification catalyst B is 10-25 percent lower than that of the hydrogenation modification catalyst A.
In the method of the invention, the reaction conditions of the hydrotreating reaction zone are as follows: the reaction pressure is 5.0-20.0 MPa, preferably 10.0-15.0 MPa; the reaction temperature is 180-400 ℃, and preferably 200-320 ℃; the volume ratio of hydrogen to oil is 300; preferably 500; the volume space velocity is 0.1 to 10.0h -1 Preferably 0.4 to 1.0h -1 。
In the method, the reaction conditions of the hydrogenation modification reaction zone are as follows: the reaction pressure is 5.0-20.0 MPa, preferably 10.0-15.0 MPa; the reaction temperature is 180-400 ℃, preferably 250-350 ℃; hydrogen to oil volume ratio 500; the volume space velocity is 0.1 to 1.5h -1 Preferably 0.5 to 1.2h -1 。
Compared with the prior art, the invention has the following advantages:
(1) In the method, the rosin uses a gas-liquid countercurrent reactor in a hydrotreating reaction zone, so that hydrogen and rosin mixed raw materials are more fully contacted, oxygen in the raw material rosin can be discharged from the upper part of the reactor together with gas in the form of water vapor after being hydrogenated, and the gas after water removal can be further used in a circulating hydrogen system, so that a set of high-fraction and low-fraction separation system can be omitted.
(2) In the method, rosin is firstly subjected to hydrofining reaction at the upper part of a hydrotreating reaction zone to remove a large amount of acid and simultaneously saturate double bonds, the temperature at the lower part of the hydrotreating reaction zone is relatively higher due to heat release of the hydrofining reaction, and the hydrofining reaction is a reversible reaction which is influenced by both thermodynamics and dynamics.
(3) The method adopts a proper high-activity and low-activity hydrogenation modification catalyst combination, most of tricyclic naphthenic hydrocarbon and bicyclic naphthenic hydrocarbon in the raw materials are converted into bicyclic naphthenic hydrocarbon and monocyclic naphthenic hydrocarbon after ring opening in a hydrogenation modification reaction zone, and the transformer oil with good low-temperature performance, rubber intersolubility, gassing property and oxidation stability can be obtained. Provides a processing method for improving the economical efficiency of the rosin with lower added value, and develops a new raw material for transformer oil. A series combination process is adopted, so that the processing raw materials, the process conditions and the catalyst of each section are reasonably matched, the activity of the catalyst is fully exerted, the product quality is ensured, and the raw material source of the transformer oil is enlarged. The light transformer oil is produced by adopting a mild rosin processing scheme for gradually removing various impurities, so that the condensation and carbon deposition of abietic acid resin in rosin at a high temperature at a single stage can be avoided, and the service life of the catalyst is seriously influenced.
Drawings
FIG. 1 is a schematic process flow diagram of the process of the present invention.
Detailed Description
The method of the present invention will be described in detail below with reference to the accompanying drawings.
As shown in figure 1, rosin 1 and a solvent 2 are mixed and filtered to obtain a material 3, the material 3 enters a reactor from the top of a hydrotreating reactor 5, contacts with hydrogen 4 entering from the bottom of the hydrotreating reactor 5 to carry out hydrogenation reaction, a gas phase effluent 7 obtained by the reaction enters a circulating hydrogen system after being dehydrated by a dehydration tank, a liquid phase effluent 6 obtained by the hydrogenation reaction enters a hydrogenation modification reaction zone 8 after being mixed with hydrogen, contacts with a hydrogenation modification catalyst B, and carries out saturated ring opening on two-ring and a small amount of tricyclic naphthenic hydrocarbon, and simultaneously, the completeness of a side chain after ring opening is kept, so that the two-ring or bicyclic naphthenic hydrocarbon with multiple side chains is obtained. The effluent 9 of the hydro-upgrading reaction enters a separation system 10, the separation system 10 generally comprises a high-pressure separator and a low-pressure separator, a gas phase 11 obtained by separation enters a circulating hydrogen system as circulating hydrogen, and a liquid-phase product 12 enters a fractionating tower 13 to be separated to obtain low-aromatic solvent oil 14 and transformer oil 15.
The present invention will be further described with reference to the following examples.
The various catalysts referred to in the examples may be selected from commercial catalysts by nature, or may be prepared as known in the art. The hydrofining catalyst can be selected from commercial catalysts such as 3936, 3996, FF-16, FF-26 and the like which are developed and produced by the comforting petrochemical research institute.
The preparation process of the hydro-upgrading catalyst comprises the following steps: amorphous silica-alumina and modified Y zeolite are mixed homogeneously, mixed with adhesive, kneaded and rolled into lump, extruded in a extruder to form carrier, and loaded with hydrogenating active metal.
The preparation method of the amorphous silica-alumina comprises the following steps:
a. preparing a sodium aluminate solution and a sodium silicate solution;
b. adding the sodium aluminate solution and the sodium silicate solution into a colloid forming tank in parallel, and simultaneously ventilating and introducing CO 2 Gas, adjusting sodium aluminate solution, sodium silicate solution and CO 2 Controlling the flow rate, controlling the pH value of the material in the gel forming tank to be 9-11, controlling the neutralization reaction temperature to be 20-50 ℃, and controlling the neutralization reaction time to be 0.5-1.5 hours;
c. under the temperature and pH value control of the step b, the mixture is ventilated and stabilized for 0.5 to 3.0 hours, preferably 0.5 to 1.0 hour;
d. c, filtering and washing the solid-liquid mixture obtained in the step c;
e. and d, drying and crushing the step d to obtain the amorphous silica-alumina.
In the step a, the concentration of the sodium aluminate solution is 25 to 60 gAl 2 O 3 Preferably 30 to 45gAl 2 O 3 (ii) the concentration of the sodium silicate solution is 100-250 g SiO 2 a/L, preferably from 100 to 150g of SiO 2 /L。
And d, filtering the slurry obtained in the step d, washing the slurry to be neutral by deionized water at 50-90 ℃, and then drying the slurry for 6-8 hours at 110-130 ℃.
The pH value in step b is generally constant at 9-11, preferably 9.5-10.5; the neutralization reaction time is generally 0.5 to 1.5 hours, preferably 45 to 60 minutes.
In step b, CO 2 The concentration is 20-50 v%. The aeration means introducing gas from the bottom of the reaction gel-forming tank to make the reaction system uniform, and introducing air or other CO-free gas 2 Of (2) is used.
The amorphous silica-alumina is prepared by taking sodium aluminate, sodium silicate and carbon dioxide as raw materials. The method is particularly suitable for manufacturers producing alumina by adopting a sintering process, and the intermediate product of the method is sodium aluminate solution and byproduct CO 2 Production of amorphous silica-alumina from gas, na produced 2 CO 3 The mother liquor may be recycled to the sintering process to provide a portion of the Na 2 CO 3 And a closed cycle is formed without generating wastewater pollution.
The modified Y zeolite is prepared by passing NaY through NH with the pH value of 1 to 3 4 + Exchange, hydrothermal treatment and acid treatment. The preparation method comprises the following specific steps:
passing the NaY zeolite through a primary NH 4 NO 3 After the exchange, oxalic acid and NH are reused 4 NO 3 Carrying out secondary NH on the mixed solution at the pH value of between 1 and 3 4 + Exchanging, then carrying out first hydrothermal treatment under the conditions of 0.080 to 0.098 MPa and 500 to 550 ℃, and carrying out NH after the first hydrothermal treatment 4 NO 3 Exchanging, and performing secondary hydrothermal treatment under the conditions of 0.1 to 0.2MPa and 500 to 700 ℃. Finally using HNO 3 And carrying out acid treatment to obtain the modified Y zeolite.
The loading method of the active metal of the hydro-upgrading catalyst can adopt the conventional technologies such as a kneading method, an impregnation method and the like, and preferably adopts a mode of firstly extruding strips and forming and then impregnating metal components. The catalyst is prepared by uniformly mixing modified Y zeolite and amorphous silica-alumina dry gel powder, adding a proper amount of adhesive prepared by peptizing SB alumina and nitric acid, kneading or rolling into paste, extruding into strips, and forming, wherein the strips are generally cylindrical strips with the diameter of 3-8 mm. The carrier is dried for 4 to 14 hours at the temperature of 100 to 130 ℃ and baked for 3 to 10 hours at the temperature of 500 to 600 ℃. After activation, the impregnating solution containing the hydrogenation metal is impregnated by saturated or excessive impregnating solution, then drying is carried out for 4 to 14 hours at the temperature of 100 to 130 ℃, and the catalyst is prepared after roasting is carried out for 3 to 10 hours at the temperature of 450 to 550 ℃.
The following examples are provided to illustrate the details and effects of the method of the present invention.
The following examples further illustrate the process provided by the present invention, but do not limit the scope of the invention. The properties of the rosin raw material treated by the method are as follows: the main component is resin acid, which accounts for about 90 percent, and the density (20 ℃): 1.081 g/cm 3 The melting point is 110-135 ℃, the softening point (ring and ball method) is 72-76 ℃, the boiling point is about 300 ℃, and the refractive index is 1.5451. The flash point (open) is 216 ℃, and the burning point is 480-500 ℃.
The following example 1 is a process for preparing amorphous silica-alumina according to the catalyst of the present invention, example 2 is a process for preparing a hydro-upgrading catalyst A, and example 3 is a process for preparing a hydro-upgrading catalyst B.
Example 1
700 solid sodium aluminate is prepared into 200gAl 2 O 3 /L concentrated sodium aluminate solution, and then diluted into 35gAl 2 O 3 Taking SiO-containing sodium aluminate working solution (a) 2 28wt% sodium silicate solution, and diluting to 150gSiO 2 2L (b) of sodium silicate working solution. Taking a 30L steel gel-forming tank, simultaneously opening the valves of the containers respectively storing (a) and (b), and simultaneously ventilating and introducing 45v% CO 2 Gas, setting the flow rates of (a) and (b) to make the reaction time at 1 hour, and rapidly adjusting CO 2 The flow rate of (a) is controlled to keep the pH value of the system at about 10.0 and the reaction temperature at 30 ℃, and after the (a) and the (b) are reacted, the introduction of CO is stopped 2 Then, it was allowed to stabilize under ventilation for 40 minutes, and the slurry was filtered and washed to neutrality with deionized water at 85 ℃. Drying at 120 deg.C for 8 hr, pulverizing, and sieving to obtain amorphous silica-alumina GL. The amorphous silica-alumina contains 30wt% of silica and has a specific surface area of 560m after activation 2 The pore volume is 1.41ml/g, the infrared acidity is 0.42mmol/g, the pore volume with the pore diameter of 4-10 nm accounts for 90 percent of the total pore volume,>the pore volume at 15nm accounts for 3% of the total pore volume.
Example 2
80g of silicon-aluminum GL and 30g of modified Y zeolite (SiO) 2 /Al 2 O 3 40, a unit cell constant of 2.432nm, and an infrared acidity of 0.19mmol/g specific surface 866m 2 0.52ml/g of pore volume) and 250g of adhesive prepared by peptizing nitric acid and SB alumina, kneading, rolling, preparing paste capable of extruding strips, and extruding and molding the strips. Drying at 110 deg.C for 6 hr, and calcining at 550 deg.C for 4 hr to obtain carrier A. And then 200ml of Mo-Mi co-immersion liquid is used for over-dipping for 80gA for 2 hours, drying is carried out for 6 hours at 110 ℃, and roasting is carried out for 4 hours at 500 ℃ to prepare the hydrogenation modified catalyst A. The physical properties of the hydroupgrading catalyst are shown in Table 1.
Example 3
100g of silicon-aluminum GL and 45g of modified Y zeolite (SiO) 2 /Al 2 O 3 40, a unit cell constant of 2.432nm, and an infrared acidity of 0.19mmol/g specific surface 866m 2 0.52ml/g of pore volume) and 310g of adhesive prepared by peptizing nitric acid and SB alumina, kneading, rolling, preparing paste capable of extruding strips, and extruding and forming the strips. Drying at 110 deg.C for 6 hr, and calcining at 550 deg.C for 4 hr to obtain carrier B. And then 200ml of Mo-Mi co-immersion liquid is used for over-dipping 80gA for 2 hours, drying is carried out for 6 hours at 110 ℃, and roasting is carried out for 4 hours at 500 ℃ to prepare the hydrogenation modified catalyst B. Physical properties of the hydro-upgrading catalyst are shown in Table 1.
TABLE 1 physical and chemical Properties of Hydroupgrading catalyst
Example 4
The hydrotreating reaction zone is filled with a hydrofining catalyst 3936 and a hydro-upgrading catalyst a, and the filling volume ratio of the hydrofining catalyst 3936 to the hydro-upgrading catalyst a is 1:1; the hydrogenation modification reaction zone is filled with a hydrogenation modification catalyst B; the process conditions and product properties of the hydrogenation process are shown in Table 2.
Comparative example 1
The same feedstock as in example 1 was used except that the hydrotreated product was not subjected to hydro-upgrading. The hydrotreating reaction zone is filled with a hydrofining catalyst 3936 and a hydro-upgrading catalyst a, and the filling volume ratio of the hydrofining catalyst 3936 to the hydro-upgrading catalyst a is 1:1. the process conditions and product properties of the hydrogenation process are shown in Table 2.
Comparative example 2
The same raw materials as in example 1 were used, except that the lower part of the hydrotreating reaction zone was not loaded with the hydro-upgrading catalyst a, the hydrotreating reaction zone was loaded with the hydrofining catalyst 3936, and the hydro-upgrading reaction zone was loaded with the hydro-upgrading catalyst B, and the process conditions and product properties during the hydrogenation process are shown in table 2.
TABLE 2 Process conditions and results of examples and comparative examples
Claims (10)
1. A method for producing special oil products by rosin hydrogenation comprises the following steps:
(1) Mixing rosin and a solvent at 130-160 ℃, filtering the mixture to be used as a raw material, feeding the raw material and hydrogen into a hydrotreating reaction zone in a gas-liquid countercurrent mode for reaction, and sequentially arranging a hydrofining catalyst and a hydro-upgrading catalyst A in the hydrotreating reaction zone according to a liquid phase flow direction;
(2) Carrying out gas-liquid separation on the reaction effluent obtained in the step (1) to obtain gas and liquid effluent, and dehydrating the obtained gas and then sending the gas to a circulating hydrogen system;
(3) Mixing the liquid effluent obtained in the step (2) with hydrogen, and then allowing the mixture to enter a hydro-upgrading reaction zone for hydro-upgrading reaction, wherein a hydro-upgrading catalyst B containing amorphous silica-alumina and modified Y zeolite is used in the hydro-upgrading reaction zone, and the hydro-upgrading reaction product is separated to obtain low aromatic solvent oil and transformer oil;
wherein, the hydro-upgrading catalyst A comprises: 10 to 35 weight percent of amorphous silica-alumina, 2 to 15 weight percent of modified Y zeolite, 20 to 50 weight percent of VIB group metal and 8 to 15 weight percent of VIII group metal calculated by oxide; the hydro-upgrading catalyst B comprises: 20 to 60 weight percent of amorphous silica-alumina, 5 to 25 weight percent of modified Y zeolite, 10 to 30 weight percent of VIB group metal and 4 to 10 weight percent of VIII group metal calculated by oxide;
compared with the hydrogenation modified catalyst B, the hydrogenation modified catalyst A has low carrier content and high hydrogenation component content;
in the step (1), the filling volume ratio of the hydrogenation refining catalyst to the hydrogenation modification catalyst A in the hydrogenation treatment reaction zone is 50:50.
2. the method of claim 1, wherein: in the step (1), the solvent is one or more of low aromatic solvent oil, F-T synthesized light distillate oil, straight-run diesel oil and hydrocracking diesel oil.
3. A method according to claim 1 or 2, characterized in that: in the step (1), the solvent is low aromatic solvent oil.
4. The method of claim 1, wherein: in the step (1), the mass ratio of the rosin to the solvent is 1:1 to 1:5.
5. the method of claim 1 or 4, wherein: in the step (1), the mass ratio of the rosin to the solvent is 1:2 to 1:3.
6. the method of claim 1, wherein: in the step (1), the rosin is resin and turpentine.
7. The method of claim 1, wherein: the reaction conditions of the hydrotreating reaction zone are as follows: the reaction pressure is 5.0-20.0 MPa, the reaction temperature is 180-400 ℃, the volume ratio of hydrogen to oil is 300 -1 。
8. The method of claim 1 or 7, wherein: the reaction conditions of the hydrotreating reaction zone are as follows: the reaction pressure is 10.0-15.0 MPa, the reaction temperature is 200-320 ℃, the volume ratio of hydrogen to oil is 500,the volume space velocity is 0.4 to 1.0h -1 。
9. The method of claim 1, wherein: the reaction conditions of the hydro-upgrading reaction zone are as follows: the reaction pressure is 5.0-20.0 MPa, the reaction temperature is 180-400 ℃, the volume ratio of hydrogen to oil is 500: 1-3000, and the volume airspeed is 0.1-1.5 h -1 。
10. A method according to claim 1 or 9, characterized in that: the reaction conditions of the hydro-upgrading reaction zone are as follows: the reaction pressure is 10.0-15.0 MPa, the reaction temperature is 250-350 ℃, the volume ratio of hydrogen to oil is 500-1.2 h -1 。
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| CN103102900A (en) * | 2011-11-10 | 2013-05-15 | 中国石油化工股份有限公司 | Hydrogenation method for producing high quality solvent oil from biological oil |
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| CN103102920A (en) * | 2011-11-10 | 2013-05-15 | 中国石油化工股份有限公司 | Two-stage hydrogenation method for producing high quality solvent oil |
| CN103102898A (en) * | 2011-11-10 | 2013-05-15 | 中国石油化工股份有限公司 | Hydrocracking method for producing low aromatic hydrocarbon solvent oil from biological oil |
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| CN103102900A (en) * | 2011-11-10 | 2013-05-15 | 中国石油化工股份有限公司 | Hydrogenation method for producing high quality solvent oil from biological oil |
| CN103102901A (en) * | 2011-11-10 | 2013-05-15 | 中国石油化工股份有限公司 | Hydrogenation method for producing low aromatic hydrocarbon solvent oil from biological oil |
| CN103102920A (en) * | 2011-11-10 | 2013-05-15 | 中国石油化工股份有限公司 | Two-stage hydrogenation method for producing high quality solvent oil |
| CN103102898A (en) * | 2011-11-10 | 2013-05-15 | 中国石油化工股份有限公司 | Hydrocracking method for producing low aromatic hydrocarbon solvent oil from biological oil |
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