TWI398510B - Method for modifying oil - Google Patents

Description

Oil product modification method

The present invention relates to a method for upgrading an oil product, and more particularly to a method for upgrading an oil product using a subcritical carbon dioxide fluid.

The hydrogenation process is one of the currently used oil upgrading methods. However, due to the high viscosity of the oil, the solubility of hydrogen in the oil is not high, and the effect of mass transfer between the gas and liquid reactants is not good. Further, when a catalyst having a pore property is used, the rate at which the oil enters the inside of the pore is slow, so that the efficiency of the hydrogenation reaction is limited. One method for increasing solubility is in a high pressure environment of greater than 2000 psi, however this requires complex and expensive high pressure equipment and consumes a large amount of hydrogen, thus causing process hazards and operating costs.

In addition, oils with high oxygen content are corrosive to the catalyst, so oil adhering to the surface of the catalyst may cause serious poisoning of the catalyst, and the oil stuck in the catalyst hole may cause the hole to be blocked. The problem is that the reaction efficiency is lowered and the quality of the upgraded oil is not good.

Therefore, there is a need to provide a method of upgrading oil products to overcome the deficiencies of the prior art.

The invention provides a method for upgrading an oil product, comprising: contacting an oil with hydrogen in a presence of a catalyst to perform a hydrodeoxygenation reaction, wherein the hydrodeoxygenation reaction is carried out in a subcritical carbon dioxide fluid.

The invention also provides a method for upgrading an oil, comprising: introducing a proportion of hydrogen and carbon dioxide into the reactor in a reactor and in the presence of a catalyst, and stabilizing the reactor The hydrogenation reaction temperature and the hydrogenation reaction pressure, the carbon dioxide is a subcritical fluid, and then the oil is injected into the reactor at a fixed flow rate to bring the oil and hydrogen into contact for the hydrodeoxygenation reaction.

The present invention provides a method for upgrading an oil product comprising contacting an oil to be treated with hydrogen in the presence of a catalyst to carry out a hydrodeoxygenation reaction, wherein the hydrogenation reaction is carried out in a subcritical carbon dioxide fluid. The use of the subcritical carbon dioxide fluid of the present invention can greatly improve the efficiency of oil upgrading.

The oil to be treated of the present invention includes, but is not limited to, biomass cracking oil, biodiesel, waste lubricating oil, waste cooking oil, plastic cracking oil or tire cracking oil. In general, oils that need to be modified have a high oxygen content (greater than 40%) and are unstable, so the quality is not good.

The formation of the secondary critical carbon dioxide fluid of the present method is primarily such that the pressure of the reaction environment is such that the carbon dioxide fluid becomes a subcritical state. Accordingly, the hydrogenation reaction has a pressure of less than about 1000 psi, preferably from about 300 psi to about 1000 psi, and a temperature of from about 300 °C to about 500 °C. Since the subcritical carbon dioxide fluid does not need to reach the critical pressure and is formed in a lower pressure environment, energy consumption and equipment cost can be reduced.

The hydrodeoxygenation reaction in the process is carried out in a subcritical carbon dioxide fluid. The subcritical carbon dioxide fluid gives the oil an expended liquid characteristic between the liquid and the gas and the viscosity is greatly reduced. When hydrogenation or hydroformylation is carried out in the expanded liquid, even if the organic solvent is not completely dissolved A homogeneous reaction is formed in carbon dioxide, but since the reaction gas can be dissolved in a liquid solvent in a large amount, the mass transfer resistance between the gas-liquid interface is effectively eliminated to improve the solubility of hydrogen, and in addition, the oil can rapidly flow through the catalyst surface or even enter the gas. Inside the hole, the effective reaction area of the catalyst is increased, and further, since the heat transfer resistance of the oil is small, the conversion efficiency of the oil is improved. In addition, since the oil does not stick to the surface of the catalyst, the problem of poisoning of the catalyst is avoided.

The process can be carried out in a reactor, such as a fixed bed reactor. The catalyst can be placed in the reactor. Preferably, the catalyst is mixed with inert quartz sand to be fixed in the reactor. In the embodiment, the catalyst particle diameter is larger than that of the quartz sand, so that the void between the catalysts can be filled with quartz sand to achieve a fixed effect. The benefits of using quartz sand also include its heat storage efficiency, which can effectively help the stability of the reactor temperature and reduce the heat loss. In addition, quartz sand can also increase the dispersion of oil when flowing through the reactor, so that the oil The mixing with the catalyst and hydrogen is more uniform and prevents product from flowing back.

The catalyst used in the method includes a metal such as platinum (Pt), palladium (Pd) or nickel-molybdenum alloy Ni-Mo. The catalyst may further use a metal oxide support such as alumina (Al ₂ O ₃ ) or zeolite (Zeolitic). The particle size of the catalyst can range from about 1 mm to about 10 mm. The size of quartz sand can range from 8mesh to 18mesh. The weight ratio of quartz sand to catalyst can range from 5:1 to 10:1.

In the process of the present invention, the hydrogenation pressure of the reactor can be controlled by introducing hydrogen and carbon dioxide into the reactor to regulate the flow of hydrogen and carbon dioxide. Preferably, the hydrogen and carbon dioxide fed to the reactor have a fixed flow ratio. The flow ratio of hydrogen to carbon dioxide can range from 1:0.1 to 1:10.

In the process of the present invention, the catalyst may be subjected to a regeneration process to increase the efficiency of the hydrogenation reaction prior to introducing hydrogen, carbon dioxide, and oil into the reactor for hydrogenation. First, the catalyst is calcined, which allows air to be introduced into the reactor for heating. The calcination step may have an air flow rate of from 80 ml/min to 220 ml/min, a calcination temperature of from 300 ° C to 600 ° C, and a calcination time of from 2 hours to 6 hours. After the calcining step, a catalyst is then subjected to a reduction step to reduce the activity of the catalyst, which can be passed through the reactor for heating. The nitrogen flow rate of the reduction step may be from 50 ml/min to 1500 ml/min, the reduction temperature may be from 200 ° C to 500 ° C, and the reduction time may be from 2 hours to 6 hours.

The above and other objects, features, and advantages of the present invention will become more apparent and understood.

[Example 1]

1 is a flow chart of a hydrodeoxygenation reaction device for oil products, wherein 1 is a hydrogen cylinder; 2 is a carbon dioxide cylinder; 4 is a mass controller; 6 is a quantitative pump; 71 and 72 are regulating valves; 8 is a storage tank; 9 is an injection pump; 10 is a buffer tank (Surge Tank); 11 is a reactor; 12 is a gas-liquid separation tank; 13 is a sampling valve; 14 is a wet flow meter; T is a thermocouple; P is a pressure detector 31, 32 and 33 are filters; 51, 52 and 53 are return valves.

Reactor 11 is a column flow fixed bed reactor. The reactor 11 was charged with a mixture of 5 g of Pt/Al ₂ O ₃ catalyst and 50 g of quartz sand. The temperature of the reactor 11 was first controlled to about 425 °C. The periphery of the reactor 11 is covered by an electrothermal high temperature furnace, and a thermocouple T is inserted therein to detect the temperature of the fluid in the reactor 11, and temperature feedback control is performed by the electric heater. Then, under the condition that the flow ratio of hydrogen and carbon dioxide is 1:1, the flow rate of hydrogen is controlled by the electronic quality controller 4, and the flow rate of carbon dioxide is controlled by the regulating valve 71, and hydrogen and carbon dioxide are mixed and then introduced into the reactor 11, and A back pressure valve connected to the outlet of the reactor 11 was used to bring the pressure in the reactor 11 to 500 psi and the pressure was stabilized. After the temperature and pressure of the reactor 11 to be stabilized, placed oleic acid _{(oleic acid; C 18 H 34} O 2) acid of a glass tank 8, the use of high pressure injection pump at a fixed flow rate of 0.5 to 9 3 ml/min access to the system. Since the injection pump used is a Lupu pump, when it is introduced into the system, it does not affect the pressure inside the system, and the reactor maintains the pressure required for the hydrogenation reaction. The reactants enter the system from the upper end of the reactor 11, and undergo hydrogenation reaction after the catalyst, and the product flows out from the lower end of the reactor 11. After flowing through the back pressure valve, the reactor 11 is reduced to normal pressure and divided into gas-liquid two phases in the gas-liquid separation tank 12, the gas is collected through the sampling valve 13, and the flow rate is recorded by the wet flow meter 14, and the liquid is cooled. Collect for analysis. After upgrading, the oxygen content of the oil is reduced by 40%, and the carbon number distribution of the oil is mostly below C6.

[Comparative Example 1]

The apparatus and process steps are the same as in Example 1, in which only hydrogen and oil are introduced into the reaction system, and no carbon dioxide fluid is introduced. After the upgrading, the oxygen content of the oil is reduced by 25%, and the carbon number distribution of the oil is mostly below C6.

[Example 2]

The same apparatus and process steps as in Example 1, wherein the temperature of the reactor 11 was controlled at about 350 ° C, the pressure was controlled at about 650 psi, and the flow ratio of hydrogen to carbon dioxide was 1:1, and hydrodeoxygenation was carried out. reaction. After the upgrading, the oxygen content of the oil is reduced by 12%, and the carbon number distribution of the oil is mostly C6 to C15.

[Comparative Example 2]

The apparatus and process steps are the same as in Example 2, in which only hydrogen and oil are introduced into the reaction system, and no carbon dioxide fluid is introduced. After upgrading, the oxygen content of the oil is reduced by 5%.

[Example 3]

The apparatus and process steps identical to those of Example 1 are the simulated oils (Tetradecane: Guaiacol; C ₇ H ₈ O ₂ ) to be placed in the acid-resistant glass storage tank 8 The volume ratio is 95:5), and the high pressure injection pump 9 is introduced into the system at a fixed flow rate of 0.5 to 3 ml/min, and the temperature of the reactor 11 is controlled at about 340 ° C, the pressure is about 650 psi, and hydrogen and carbon dioxide are used. The hydrodeoxygenation reaction was carried out under a flow ratio of 1:1. After upgrading, the oxygen content of the oil decreased by 4.6%.

[Embodiment 4]

The apparatus and process steps are the same as in Example 3, in which the temperature of the reactor 11 is controlled at about 350 °C. After the upgrading, the oxygen content of the oil was reduced by 17.8%.

[Embodiment 5]

The apparatus and process steps are the same as in Example 3, in which the temperature of the reactor 11 is controlled at about 400 °C. After the upgrading, the oxygen content of the oil was reduced by 20.2%.

While the invention has been described above in terms of several preferred embodiments, it is not intended to limit the scope of the present invention, and any one of ordinary skill in the art can make any changes without departing from the spirit and scope of the invention. And the scope of the present invention is defined by the scope of the appended claims.

1. . . Hydrogen cylinder

2. . . Carbon dioxide cylinder

4. . . Quality controller

6. . . Quantitative pumping

71. . . Regulating valve

72. . . Regulating valve

8. . . Storage tank

9. . . Injection pump

10. . . Buffer tank

11. . . reactor

12. . . Gas-liquid separation tank

13. . . Sampling valve

14. . . Wet flow meter

31. . . filter

32. . . filter

33. . . filter

51. . . Check valve

52. . . Check valve

53. . . Check valve

T. . . Thermocouple

P. . . Pressure detector

Figure 1 is a schematic view of a hydrodeoxygenation reaction apparatus according to an embodiment of the present invention.

1. . . Hydrogen cylinder

2. . . Carbon dioxide cylinder

4. . . Quality controller

6. . . Quantitative pumping

71. . . Regulating valve

72. . . Regulating valve

8. . . Storage tank

9. . . Injection pump

10. . . Buffer tank

11. . . reactor

12. . . Gas-liquid separation tank

13. . . Sampling valve

14. . . Wet flow meter

31. . . filter

32. . . filter

33. . . filter

51. . . Check valve

52. . . Check valve

53. . . Check valve

T. . . Thermocouple

P. . . Pressure detector

Claims (13)

An oil upgrading method comprising: contacting an oil with hydrogen in a presence of a catalyst for hydrodeoxygenation reaction at a temperature between 300 ° C and 500 ° C and a pressure less than 1000 psi The secondary carbon dioxide fluid is carried out; wherein the catalyst comprises a metal, and wherein the oil comprises a biomass cracking oil, a biodiesel, a waste lubricating oil, a waste cooking oil, a plastic cracking oil or a tire cracking oil. The method for upgrading an oil product according to claim 1, wherein the hydrogenation reaction is carried out in a column flow fixed bed reactor. The method for upgrading an oil product according to claim 2, wherein the hydrogen gas and the carbon dioxide are first introduced into the reactor at a fixed flow rate, and the temperature and pressure of the reactor are stabilized, and then A fixed flow rate is injected into the reactor. The method for upgrading an oil product according to claim 1, wherein the hydrodeoxygenation reaction has a pressure of from 300 psi to 1000 psi. The method for upgrading an oil product according to claim 1, wherein the flow ratio of the hydrogen to the carbon dioxide is between 1:0.1 and 1:10. The method for upgrading an oil product according to claim 1, further comprising regenerating the catalyst before performing the hydrodeoxygenation reaction. The method for upgrading an oil product according to claim 6, wherein the regenerating step comprises: performing a first heating step on the catalyst under an air atmosphere; The catalyst is subjected to a second heating step under a nitrogen atmosphere. The method for modifying an oil product according to claim 7, wherein the air flow rate of the first heating step is between 80 ml/min and 220 ml/min, and the temperature is between 300 ° C and 600 ° C, time. The system is between 2 hours and 6 hours. The method for modifying an oil product according to claim 7, wherein the nitrogen flow rate of the second heating step is between 50 ml/min and 1500 ml/min, and the temperature system is between 200 ° C and 500 ° C. The system is between 2 hours and 6 hours. A method for upgrading an oil product comprises: introducing hydrogen and carbon dioxide into a reactor in the presence of a catalyst, causing the reactor to have a hydrodeoxygenation reaction pressure, and injecting the oil into the reactor at a fixed flow rate Wherein the oil and hydrogen are contacted for a hydrodeoxygenation reaction, wherein the carbon dioxide is a subcritical fluid having a temperature between 300 ° C and 500 ° C and a pressure of less than 1000 psi; wherein the catalyst comprises a metal, and wherein the oil comprises Biomass cracking oil, biodiesel, waste lubricating oil, waste cooking oil, plastic cracking oil or tire cracking oil. The method for upgrading an oil product according to claim 10, wherein the reactor comprises a column flow fixed bed reactor. The method for upgrading an oil product according to claim 10, wherein the hydrodeoxygenation reaction has a pressure of from 300 psi to 1000 psi. The method for upgrading an oil product according to claim 10, wherein the flow ratio of the hydrogen to the carbon dioxide is between 1:0.1 and 1:10.