Method for reducing viscosity of residual oil through synergism of emulsification and hydrothermal catalytic cracking

Abstract

The invention belongs to the technical field of residual oil viscosity reduction methods, and discloses a method for reducing residual oil viscosity through synergism of emulsification and hydrothermal catalytic cracking. The method comprises the following steps: emulsifying residual oil, an emulsifier, a co-emulsifier, a stabilizer and water to obtain emulsified residual oil; and carrying out hydrothermal catalytic cracking on the emulsified residual oil and a catalyst to obtain viscosity-reduced residual oil. According to the method, the residual oil and water are in full contact, and the purpose of improving the hydrothermal catalytic cracking viscosity reduction rate of the residual oil is achieved by regulating and controlling emulsification conditions (oil-water ratio, shearing speed and the like) and regulating the dosage ratio of each aid. According to the method for treating residual oil before emulsification, oil and water can be fully contacted and reacted by increasing the contact area of the oil and the water, and the viscosity reduction efficiency of the catalytic reaction of hydrothermal catalytic cracking is improved.

Description

Technical Field

[0001] The invention relates to the technical field of residual oil viscosity reduction methods, and in particular to a method for synergistically reducing residual oil viscosity by emulsification and hydrothermal catalytic cracking. Background Art

[0002] At present, with the development and consumption of crude oil, the exploitation and utilization of oil and gas resources, especially the utilization of unconventional resources, need to be highly valued. Residue oil is the residue produced in the process of oil refining. It is the residual oil extracted from the bottom of the vacuum tower of the refinery after the crude oil is distilled under normal and vacuum conditions. Residue oil accounts for a high proportion of crude oil in most important oil fields, but its actual utilization rate is low. The biggest factor affecting the utilization rate of residue oil is its high density, high viscosity, poor fluidity and other characteristics. Therefore, the benefits brought by reducing the viscosity of residue oil for subsequent transportation, storage and processing cannot be underestimated.

[0003] Traditional viscosity reduction methods include chemical viscosity reduction and physical viscosity reduction. Heating viscosity reduction is currently the most common chemical viscosity reduction method, but it consumes a lot of energy and causes a lot of oil loss. Blending viscosity reduction is to add a certain amount of light oil to heavy oil to reduce the viscosity of heavy oil. Although this method consumes less energy, the subsequent pipeline construction and operation costs are relatively expensive, which increases industrial costs. As a relatively new viscosity reduction technology, the residue oil hydrogenation process can improve the shortcomings of traditional viscosity reduction methods. Residue oil hydrocracking, catalytic cracking and other technologies can decompose residue oil into smaller molecules, reduce the content of impurities such as sulfur and nitrogen, and greatly reduce the viscosity of residue oil, and even make common chemical raw materials such as automotive oil products. However, these technologies have problems such as high energy consumption, short catalyst life, and catalyst poisoning. Hydrothermal catalytic cracking technology is a relatively new non-hydrogenated residue oil processing technology. It uses high temperature and high pressure water and catalysts to decompose residue oil into smaller molecules, greatly reducing the viscosity of residue oil. Compared with traditional residue oil hydrocracking, catalytic cracking and other technologies, hydrothermal catalytic cracking technology has the advantages of low reaction temperature, low energy consumption and wide product distribution. It is an environmentally friendly and efficient residue oil processing technology.

[0004] However, a large amount of catalyst and water are required in the hydrothermal catalytic cracking reaction process, which results in high cost. In addition, the water and oil cannot fully contact during the reaction, resulting in low catalytic effect of the catalyst, which causes excess and waste of catalyst and increases the reaction cost. Therefore, the art urgently needs to develop a method for reducing the viscosity of residual oil by hydrothermal catalytic cracking with low cost and high catalytic efficiency. Summary of the invention

[0005] The purpose of the present invention is to provide a method for synergistically reducing the viscosity of residual oil by emulsification and hydrothermal catalytic cracking, so as to solve the problem that a large amount of catalyst and water are required in the current hydrothermal catalytic cracking reaction process, resulting in high cost, and the water and oil cannot fully contact during the reaction process, resulting in low catalytic effect of the catalyst, causing excess and waste of catalyst, and increasing reaction cost.

[0006] In order to achieve the above object, the present invention adopts the following technical solution:

[0007] The present invention provides a method for synergistically reducing the viscosity of residual oil by emulsification and hydrothermal catalytic cracking, comprising the following steps:

[0008] The residual oil, emulsifier, co-emulsifier, stabilizer and water are emulsified to obtain emulsified residual oil; the emulsified residual oil and catalyst are subjected to hydrothermal catalytic cracking to obtain the residual oil with reduced viscosity.

[0009] Preferably, the viscosity of the residual oil at 100° C. is ≥8000 mPa·s.

[0010] Preferably, the emulsifier is one or more of sodium oleate, potassium oleate, polyoxyethylene monostearate and sodium N-hexadecyl-N-ethylmorpholinyl ethyl sulfate.

[0011] Preferably, the auxiliary emulsifier is one or more of n-butanol, ethylene glycol, glycerol pentaerythritol and sorbitan.

[0012] Preferably, the stabilizer is one or more of oxalic acid, citric acid and triethanolamine.

[0013] Preferably, the catalyst is one or more of cobalt naphthenate, zinc naphthenate, iron naphthenate and manganese naphthenate.

[0014] Preferably, the mass ratio of the residual oil, emulsifier, co-emulsifier, stabilizer, water and catalyst is 25-30:0.1-1:0.1-1:0-1:7-9:0.2-2.

[0015] Preferably, the specific steps of emulsification are: mixing the emulsifier, the co-emulsifier, the stabilizer and water and adding them into the stirred residual oil; the stirring speed is ≥200r / min, the stirring temperature is 80-100°C, and the stirring time is 20-30min.

[0016] Preferably, the emulsification temperature is 80-100° C., the emulsification shear speed is 4500-6000 r / min, and the emulsification time is 10-20 min.

[0017] Preferably, the temperature of the hydrothermal catalytic cracking is 330-350° C., the pressure of the hydrothermal catalytic cracking is 2-4 MPa, and the time of the hydrothermal catalytic cracking is 2-3 h.

[0018] It can be seen from the above technical solution that compared with the prior art, the present invention has the following beneficial effects:

[0019] (1) The emulsification of the present invention increases the contact area between the residual oil and water, so that the residual oil and water can fully contact and react, which can reduce the amount of water used, thereby reducing industrial costs;

[0020] (2) The method of the present invention improves the catalytic effect of the hydrothermal catalytic cracking reaction, enables the catalyst to better exert its catalytic effect, reduces the amount of catalyst used, and reduces the catalyst cost;

[0021] (3) The process of the method of the present invention is simple and efficient, with low energy consumption, small equipment requirements, low investment cost, and is conducive to industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on the provided drawings without paying creative work.

[0023] Figure 1 A process flow chart of a method for synergistically reducing the viscosity of residual oil by emulsification and hydrothermal catalytic cracking. DETAILED DESCRIPTION

[0024] The present invention provides a method for synergistically reducing the viscosity of residual oil by emulsification and hydrothermal catalytic cracking, comprising the following steps:

[0025] The residual oil, emulsifier, co-emulsifier, stabilizer and water are emulsified to obtain emulsified residual oil; the emulsified residual oil and catalyst are subjected to hydrothermal catalytic cracking to obtain the residual oil with reduced viscosity.

[0026] In the present invention, the viscosity of the residual oil at 100° C. is preferably ≥8000 mPa·s, and more preferably 8500-9000 mPa·s; the residual oil is a black solid at room temperature.

[0027] In the present invention, the emulsifier is preferably one or more of sodium oleate, potassium oleate, polyoxyethylene monostearate and sodium N-hexadecyl-N-ethylmorpholinyl ethyl sulfate.

[0028] In the present invention, the auxiliary emulsifier is preferably one or more of n-butanol, ethylene glycol, glycerol pentaerythritol and sorbitan.

[0029] In the present invention, the stabilizer is preferably one or more of oxalic acid, citric acid and triethanolamine.

[0030] In the present invention, the catalyst is preferably one or more of cobalt naphthenate, zinc naphthenate, iron naphthenate and manganese naphthenate.

[0031] In the present invention, the mass ratio of the residual oil, emulsifier, co-emulsifier, stabilizer, water and catalyst is preferably 25-30: 0.1-1: 0.1-1: 0-1: 7-9: 0.2-2, and more preferably 26-29: 0.2-0.5: 0.2-0.4: 0.18-0.3: 7.5-8.5: 0.5-0.8.

[0032] In the present invention, the specific steps of emulsification are: mixing an emulsifier, an emulsifier co-emulsifier, a stabilizer and water and adding the mixture to the stirred residual oil; the stirring speed is preferably ≥200 r / min, more preferably 300-500 r / min; the stirring temperature is preferably 80-100°C, more preferably 90-95°C; the stirring time is preferably 20-30 min, more preferably 25-28 min.

[0033] In the present invention, the emulsification temperature is preferably 80-100°C, more preferably 90-95°C; the emulsification shear speed is preferably 4500-6000r / min, more preferably 5000-5500r / min; the emulsification time is preferably 10-20min, more preferably 15-18min.

[0034] In the present invention, the temperature of the hydrothermal catalytic cracking is preferably 330-350°C, and more preferably 335-340°C; when the temperature of the hydrothermal catalytic cracking is higher than 350°C, the organic ligand of the catalyst will change, which is not conducive to the hydrothermal catalytic cracking reaction. At the same time, carrying out the hydrothermal catalytic cracking reaction at a low temperature of 330-350°C can reduce equipment loss and reduce economic costs; the pressure of the hydrothermal catalytic cracking is preferably 2-4MPa, and more preferably 3MPa; the time of the hydrothermal catalytic cracking is preferably 2-3h, and more preferably 2.5h.

[0035] The technical solutions provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0036] The viscosity of the residual oil used in the following examples and comparative examples at 100° C. is 8787 mPa·s.

[0037] Example 1

[0038] 0.17g of sodium oleate, 0.2g of n-butanol, 0.18g of triethanolamine and 7.93g of water were mixed to obtain a mixed liquid; 26.57g of oil residue was stirred at a speed of 300r / min and a temperature of 90°C for 20min to make the oil residue have microfluidity, and then the mixed liquid was added to the stirred oil residue, and emulsified at a temperature of 90°C and a shear speed of 5000r / min for 20min to obtain emulsified residual oil; the emulsified residual oil and 0.5g of ferric cyclopentaneate were placed in a quartz-lined reactor and subjected to hydrothermal catalytic cracking for 2h at a temperature of 340°C and a pressure of 3MPa to obtain a residual oil after viscosity reduction, and the viscosity of the residual oil after viscosity reduction at 100°C was measured.

[0039] Example 2

[0040] 0.38g sodium oleate, 0.2g n-butanol, 0.18g triethanolamine and 8.67g water were mixed to obtain a mixed liquid; 29.03g oil residue was stirred at a speed of 300r / min and a temperature of 90°C for 20min to make the oil residue have microfluidity, and then the mixed liquid was added to the stirred oil residue, and emulsified at a temperature of 90°C and a shear speed of 5000r / min for 20min to obtain emulsified residual oil; the emulsified residual oil and 0.5g ferric cyclopentaneate were placed in a quartz-lined reactor and subjected to hydrothermal catalytic cracking for 2h at a temperature of 340°C and a pressure of 3MPa to obtain a residual oil after viscosity reduction, and the viscosity of the residual oil after viscosity reduction at 100°C was measured.

[0041] Example 3

[0042] 0.19 g of sodium oleate, 0.19 g of n-butanol and 8.6 g of water were mixed to obtain a mixed liquid; 28.8 g of oil residue was stirred at a speed of 300 r / min and a temperature of 90°C for 20 min to make the oil residue have microfluidity, and then the mixed liquid was added to the stirred oil residue, and emulsified at a temperature of 90°C and a shear speed of 5000 r / min for 20 min to obtain emulsified residual oil; the emulsified residual oil and 0.5 g of ferric cyclopentaneate were placed in a quartz-lined reactor and subjected to hydrothermal catalytic cracking for 2 h at a temperature of 340°C and a pressure of 3 MPa to obtain a residual oil after viscosity reduction, and the viscosity of the residual oil after viscosity reduction at 100°C was measured.

[0043] Example 4

[0044] 0.18g sodium oleate, 0.18g n-butanol, 0.18g triethanolamine and 8.21g water were mixed to obtain a mixed liquid; 27.49g oil residue was stirred at a speed of 300r / min and a temperature of 90°C for 20min to make the oil residue have microfluidity, and then the mixed liquid was added to the stirred oil residue, and emulsified at a temperature of 90°C and a shear speed of 5000r / min for 20min to obtain emulsified residual oil; the emulsified residual oil and 0.5g ferric cyclopentaneate were placed in a quartz-lined reactor and subjected to hydrothermal catalytic cracking for 2h at a temperature of 340°C and a pressure of 3MPa to obtain a residual oil after viscosity reduction, and the viscosity of the residual oil after viscosity reduction at 100°C was measured.

[0045] Example 5

[0046] 0.19g of sodium oleate, 0.36g of n-butanol, 0.18g of triethanolamine and 8.67g of water were mixed to obtain a mixed liquid; 29.03g of oil residue was stirred at a speed of 300r / min and a temperature of 90°C for 20min to make the oil residue have microfluidity, and then the mixed liquid was added to the stirred oil residue, and emulsified at a temperature of 90°C and a shear speed of 5000r / min for 20min to obtain emulsified residual oil; the emulsified residual oil and 0.5g of ferric cyclopentaneate were placed in a quartz-lined reactor and subjected to hydrothermal catalytic cracking for 2h at a temperature of 340°C and a pressure of 3MPa to obtain a residual oil after viscosity reduction, and the viscosity of the residual oil after viscosity reduction at 100°C was measured.

[0047] Comparative Example 1

[0048] The difference from Example 1 is that the amount of sodium oleate used is 0.05 g, and the rest is the same as Example 1.

[0049] Comparative Example 2

[0050] The difference from Example 1 is that the amount of sodium oleate used is 0.06 g, and the rest is the same as Example 1.

[0051] Comparative Example 3

[0052] The difference from Example 1 is that n-butanol and triethanolamine are not added, and the rest are the same as Example 1.

[0053] The viscosity of the residual oil after viscosity reduction obtained in Examples 1 to 5 and Comparative Examples 1 to 3 at 100° C. is shown in Table 1.

[0054] Table 1 Viscosity of the residual oil after viscosity reduction obtained in Examples 1 to 5 and Comparative Examples 1 to 3 at 100°C

[0055]

[0056] It can be seen from Table 1 that the method of the present invention can significantly reduce the viscosity of the residual oil, and the viscosity reduction rate of the residual oil can reach 67.36-78.67%.

[0057] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A method for synergistically reducing the viscosity of residual oil by emulsification and hydrothermal catalytic cracking, characterized in that: The steps include: The residual oil, emulsifier, co-emulsifier, stabilizer and water are emulsified to obtain emulsified residual oil; the emulsified residual oil and catalyst are subjected to hydrothermal catalytic cracking to obtain the residual oil with reduced viscosity.

2. The method for synergistically reducing the viscosity of residual oil by emulsification and hydrothermal catalytic cracking according to claim 1, characterized in that: The viscosity of the residual oil at 100° C. is ≥8000 mPa·s.

3. The method for synergistically reducing the viscosity of residual oil by emulsification and hydrothermal catalytic cracking according to claim 2, characterized in that: The emulsifier is one or more of sodium oleate, potassium oleate, polyoxyethylene monostearate and sodium N-hexadecyl-N-ethylmorpholinyl ethyl sulfate.

4. The method for synergistically reducing the viscosity of residual oil by emulsification and hydrothermal catalytic cracking according to any one of claims 1 to 3, characterized in that: The auxiliary emulsifier is one or more of n-butanol, ethylene glycol, glycerol pentaerythritol and sorbitan.

5. The method for synergistically reducing the viscosity of residual oil by emulsification and hydrothermal catalytic cracking according to claim 4, characterized in that: The stabilizer is one or more of oxalic acid, citric acid and triethanolamine.

6. The method for synergistically reducing the viscosity of residual oil by emulsification and hydrothermal catalytic cracking according to claim 1 or 5, characterized in that: The catalyst is one or more of cobalt naphthenate, zinc naphthenate, iron naphthenate and manganese naphthenate.

7. The method for synergistically reducing the viscosity of residual oil by emulsification and hydrothermal catalytic cracking according to claim 6, characterized in that: The mass ratio of the residual oil, emulsifier, co-emulsifier, stabilizer, water and catalyst is 25-30:0.1-1:0.1-1:0-1:7-9:0.2-2.

8. The method for synergistically reducing the viscosity of residual oil by emulsification and hydrothermal catalytic cracking according to claim 7, characterized in that: The specific steps of the emulsification are: mixing the emulsifier, the auxiliary emulsifier, the stabilizer and water and adding them into the stirred residual oil; the stirring speed is ≥200r / min, the stirring temperature is 80-100°C, and the stirring time is 20-30min.

9. The method for synergistically reducing the viscosity of residual oil by emulsification and hydrothermal catalytic cracking according to claim 8, characterized in that: The emulsification temperature is 80-100° C., the emulsification shear speed is 4500-6000 r / min, and the emulsification time is 10-20 min.

10. The method for synergistically reducing the viscosity of residual oil by emulsification and hydrothermal catalytic cracking according to claim 8 or 9, characterized in that: The temperature of the hydrothermal catalytic cracking is 330-350° C., the pressure of the hydrothermal catalytic cracking is 2-4 MPa, and the time of the hydrothermal catalytic cracking is 2-3 hours.

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