阅读说明：本技术 用于重油催化裂化加工的重油乳液、其制法及应用 (Heavy oil emulsion for heavy oil catalytic cracking processing, preparation method and application thereof ) 是由 许晓斌 许金山 刘爱华 韩新竹 郝连峰 高隆伟 于 2018-09-05 设计创作，主要内容包括：本发明属于石油炼制的催化裂化技术领域,具体涉及一种用于重油催化裂化加工的重油乳液、其制法及应用。乳化剂与水混合后作为分散相,重油作为连续相,采用无机单分散多孔膜为乳化介质,分散相和连续相分别位于无机单分散多孔膜两侧,分散相压力为1.0-2.8MPa,重油压力为0.8-1.7MPa,分散相比连续相压力高0.2-2.0MPa,在此压力差作用下,分散相通过无机单分散多孔膜上的膜孔进入连续相,分散相在连续相的连续剪切力作用下形成均匀的油包水型乳液。本发明形成的油包水型乳液液滴大小均匀,改善了催化裂化进料的分散性和雾化程度,提高裂化深度,改善催化装置的产品分布和提高收率；本发明还提供其制备方法和应用。(The invention belongs to the technical field of catalytic cracking of petroleum refining, and particularly relates to a heavy oil emulsion for processing heavy oil by catalytic cracking, and a preparation method and application thereof. The emulsifier is mixed with water to be used as a disperse phase, the heavy oil is used as a continuous phase, the inorganic monodisperse porous membrane is used as an emulsion medium, the disperse phase and the continuous phase are respectively positioned at two sides of the inorganic monodisperse porous membrane, the pressure of the disperse phase is 1.0-2.8MPa, the pressure of the heavy oil is 0.8-1.7MPa, and the pressure of the disperse phase is 0.2-2.0MPa higher than that of the continuous phase. The water-in-oil emulsion formed by the invention has uniform droplet size, improves the dispersibility and atomization degree of catalytic cracking feed, improves the cracking depth, improves the product distribution of a catalytic device and improves the yield; the invention also provides a preparation method and application thereof.)

1. A heavy oil emulsion for catalytic cracking processing of heavy oil, characterized by: the emulsifier is mixed with water to be used as a dispersion phase, the heavy oil is used as a continuous phase, the inorganic monodisperse porous membrane is used as an emulsifying medium, the dispersion phase and the continuous phase are respectively positioned at two sides of the inorganic monodisperse porous membrane, the pressure of the dispersion phase is 0.2-2.0MPa higher than that of the continuous phase, under the action of the pressure difference, the dispersion phase enters the continuous phase through membrane pores on the inorganic monodisperse porous membrane, and the dispersion phase forms uniform water-in-oil emulsion under the action of continuous shearing force of the continuous phase.

2. A heavy oil emulsion for use in catalytic cracking processing of heavy oil according to claim 1, wherein: the pressure of a dispersed phase is 1.0-2.8MPa, and the temperature of the dispersed phase is 80-130 ℃; the pressure of the continuous phase is 0.8-1.7MPa, and the temperature of the continuous phase is 70-160 ℃.

3. A heavy oil emulsion for use in catalytic cracking processing of heavy oil according to claim 1, wherein: the emulsion droplet particle diameter of the water-in-oil emulsion is 1-10 um.

4. A heavy oil emulsion for use in catalytic cracking processing of heavy oil according to claim 1, wherein: the water in the dispersed phase accounts for 0.5-10 wt% of the heavy oil.

5. A heavy oil emulsion for use in catalytic cracking processing of heavy oil according to claim 1, wherein: the inorganic monodisperse porous membrane is a metal membrane, a glass membrane, an alumina membrane, an alloy membrane or a ceramic membrane adopting a metal support body, and the aperture of the membrane pore is 4-100 nm.

6. A heavy oil emulsion for use in catalytic cracking processing of heavy oil according to claim 1, wherein: the emulsifier is one or a mixture of several of nonionic surfactants and alcohol amine surfactants or lower saturated monohydric alcohol; the content of the emulsifier in the dispersed phase was 400-800 ppm.

7. A heavy oil emulsion for use in catalytic cracking processing of heavy oil according to claim 6, wherein: the emulsifier is prepared from polyoxyethylene sorbitan fatty acid ester, triethanolamine and ethanol according to the mass ratio of 35-35.5: 35-35.5: 30-30.5: 5.

8. A method for preparing a heavy oil emulsion for heavy oil catalytic cracking process as recited in any one of claims 1 to 7, wherein: the method comprises the following steps:

the emulsifier is mixed with water to be used as a disperse phase, the heavy oil is used as a continuous phase, the inorganic monodisperse porous membrane is used as an emulsion medium, the disperse phase and the continuous phase are respectively positioned at two sides of the inorganic monodisperse porous membrane, the pressure of the disperse phase is 1.0-2.8MPa, the pressure of the heavy oil is 0.8-1.7MPa, and the pressure of the disperse phase is 0.2-2.0MPa higher than that of the continuous phase.

9. Use of a heavy oil emulsion according to any one of claims 1 to 7 for catalytic cracking processing of heavy oil, characterized in that: the homogeneous water-in-oil emulsion is used as the feed material to carry out the catalytic cracking reaction, the reaction temperature of the catalytic cracking reaction is 450-530 ℃, and the regeneration temperature is 630-700 ℃.

10. Use of a heavy oil emulsion for catalytic cracking processing of heavy oil according to claim 9, characterized in that: the catalyst for catalytic cracking reaction is an industrial conventional catalytic cracking catalyst, and the weight ratio of the catalyst to the heavy oil is 2.0-20.0.

Technical Field

The invention belongs to the technical field of catalytic cracking of petroleum refining, and particularly relates to a heavy oil emulsion for processing heavy oil by catalytic cracking, and a preparation method and application thereof.

Background

With the decreasing of conventional petroleum resources, the degree of crude oil heaviness and deterioration is increasing. Catalytic cracking is an important means for the conversion of heavy oil into light oil, and in recent years, the proportion of heavy raw materials in catalytic cracking raw materials is increased year by year, and how to improve the yield of light oil and reduce the yield of coke and dry gas is a main problem which catalytic cracking is always required to solve. However, in the catalytic cracking reaction of heavy oil, the heavy oil is in a gas-liquid phase mixed state, so that the atomization and vaporization processes before contacting with the catalyst particles play an important role in the whole reaction.

The emulsified raw material is used as the feed of catalytic cracking reaction, the tiny water drops wrapped in emulsified heavy oil contact with a high-temperature catalyst, and are vaporized by heating to generate micro explosion or secondary explosion atomization, so that the oil drops are exploded instantly, the atomization effect is enhanced, the contact area of the atomized raw material and the catalyst is greatly increased, the distribution of the raw material on the catalyst is more uniform, and the purposes of increasing the reaction depth, improving the product distribution and increasing the target product yield are achieved.

The common emulsification methods are mainly as follows: mechanical stirring emulsification, ultrasonic emulsification, static mixer emulsification and the like, but the emulsification of the traditional method has the defects of complex emulsification device, low emulsification efficiency, high energy consumption, high operation and maintenance cost and the like, and the emulsion prepared by the traditional mechanical stirring emulsification technology has uneven liquid drop distribution, is easy to cause emulsion aggregation and oil-water separation, and restricts and strengthens the reaction process. The patent of publication No. CN102010743B discloses a method for emulsifying continuous feeding of heavy oil catalytic cracking raw materials, which mixes and emulsifies the catalytic cracking raw materials with a compound emulsifier and water and then feeds the mixture into a catalytic cracking device.

The membrane emulsification technology has the characteristics of low energy consumption, low shearing force, small dosage of surfactant, uniform emulsion particles and the like, and is widely applied to research and application of preparation of oil-in-water, water-in-oil-in-water and oil-in-water-in-oil emulsion. However, the catalytic cracking raw material belongs to heavy oil, so that the viscosity is high, the fluidity is poor, and the rapid emulsification difficulty is high by using a common membrane emulsification technology. The publication No. CN106635131A discloses a method for preparing emulsified heavy oil, which uses a ceramic membrane as an emulsifying medium, reduces the surface energy of the ceramic membrane by wetting the ceramic membrane in a dispersion phase, dissolves an emulsifier in water as the dispersion phase, uses the heavy oil as a continuous phase, and forms micro-jet by pressing the dispersion phase through the ceramic membrane under transmembrane pressure difference to form the emulsified heavy oil. However, the temperature of heavy oil in the patent is lower than the preheating temperature of catalytic cracking raw materials, and the ceramic membrane needs to be wetted in the dispersed phase for 6-12 hours to reduce the surface energy of the dispersed phase side, so that the patent is not beneficial to industrial application. The method and the embodiments disclosed by the method can be used for preparing various heavy oil emulsions, the emulsion state can not be kept stable at 190-260 ℃ of the preheating temperature of the catalytic cracking raw material, the heavy oil emulsion is broken, the pressure of a raw material system is increased due to the aggregation and vaporization of water drops, the pressure fluctuation of a reactor nozzle is large, the stability of a catalytic cracking reaction system is influenced, the catalyst is inactivated, the strength is reduced, and the like, and the method can not be applied to catalytic cracking.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide the heavy oil emulsion for heavy oil catalytic cracking processing, which has low energy consumption and good emulsification effect, the size of the formed water-in-oil emulsion liquid drop is uniform, the particle size range is about 1-10um, the dispersity and the atomization degree of catalytic cracking feed are improved, the cracking depth is improved, and the purposes of improving the product distribution of a catalytic device and improving the yield of target products are achieved; the invention also provides a preparation method of the compound, which is simple and feasible and is convenient for large-scale application in industrial production; the invention also provides the application thereof.

The heavy oil emulsion for heavy oil catalytic cracking processing of the invention adopts an emulsifier and water mixed as a dispersion phase, heavy oil as a continuous phase, an inorganic monodisperse porous membrane as an emulsion medium, the dispersion phase and the continuous phase are respectively positioned at two sides of the inorganic monodisperse porous membrane, the pressure of the dispersion phase is 0.2-2.0MPa higher than that of the continuous phase, under the action of the pressure difference, the dispersion phase enters the continuous phase through membrane pores on the inorganic monodisperse porous membrane, and the dispersion phase forms uniform water-in-oil emulsion under the action of continuous shearing force of the continuous phase.

Wherein:

the pressure of a dispersed phase is 1.0-2.8MPa, and the temperature of the dispersed phase is 80-130 ℃; the pressure of the continuous phase is 0.8-1.7MPa, and the temperature of the continuous phase is 70-160 ℃.

Continuous phase pressure of 0.8-1.7MPa, preferably 1.1-1.5MPa, preferably 1.4MPa, temperature of 70-160 deg.C, preferably 80-130 deg.C, preferably 120 deg.C; the dispersed phase pressure is 1.0-2.8MPa, preferably 1.3-2.0MPa, most preferably 1.8MPa, and the temperature is 80-130 deg.C, preferably 90-110 deg.C, most preferably 95 deg.C.

The water in the dispersed phase is present in an amount of 0.5% to 10%, preferably 1% to 5%, most preferably 2% by weight of the heavy oil.

The emulsion droplet particle diameter of the water-in-oil emulsion is 1-10 um.

The inorganic monodisperse porous membrane is a metal membrane, a glass membrane, an alumina membrane, an alloy membrane or a ceramic membrane using a metal support, preferably an alumina membrane, and the pore diameter of the membrane pores is 4 to 100nm, preferably 50 nm.

The emulsifier is one or a mixture of several of nonionic surfactants and alcohol amine surfactants or lower saturated monohydric alcohol; the emulsifier is one or a mixture of several of nonionic surfactants such as polysorbate (polyoxyethylene sorbitan fatty acid ester), sorbitan fatty acid ester, fatty alcohol-polyoxyethylene ether and the like, alcohol amine surfactants (including monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine and the like) and lower saturated monohydric alcohol (including methanol, ethanol, n-propanol, n-butanol and the like), but is not limited to the surfactants listed above; preferably, the emulsifier accounts for 35-70% and the alcohol amine surfactant accounts for 30-65% of the total mass of 100%. More preferably, the emulsifier is prepared from polyoxyethylene sorbitan fatty acid ester, triethanolamine and ethanol according to the mass ratio of 35: 35: 30: 5. The content of the emulsifier in the dispersed phase is 400-800ppm, preferably 400-600ppm, and most preferably 500 ppm.

The preparation method of the heavy oil emulsion for heavy oil catalytic cracking processing comprises the following steps: the emulsifier is mixed with water to be used as a disperse phase, the heavy oil is used as a continuous phase, the inorganic monodisperse porous membrane is used as an emulsion medium, the disperse phase and the continuous phase are respectively positioned at two sides of the inorganic monodisperse porous membrane, the pressure of the disperse phase is 1.0-2.8MPa, the pressure of the heavy oil is 0.8-1.7MPa, and the pressure of the disperse phase is 0.2-2.0MPa higher than that of the continuous phase.

The application of the heavy oil emulsion for heavy oil catalytic cracking processing of the invention is to carry out catalytic cracking reaction by taking uniform water-in-oil emulsion as a feed material, wherein the reaction temperature of the catalytic cracking reaction is 450-530 ℃, and the regeneration temperature is 630-700 ℃.

The catalyst for catalytic cracking reaction is an industrial conventional catalytic cracking catalyst, and the weight ratio of the catalyst to the heavy oil is 2.0-20.0.

Compared with the prior art, the invention has the following advantages:

(1) the invention adopts inorganic monodisperse porous membrane to emulsify and catalyze raw materials, has high emulsification efficiency, low energy consumption and good emulsification effect, forms the water-in-oil emulsion with uniform droplet size, has the particle size range of about 1-10um, is simple and easy to operate, and is convenient for large-scale application in industrial production.

(2) The invention adopts inorganic monodisperse porous membrane as emulsifying medium, catalytic cracking raw material as continuous phase and water as disperse phase, which pass through the membrane pores under higher pressure difference and form uniform water-in-oil emulsion under the action of continuous phase high flow rate shearing force, thereby improving the dispersibility and atomization degree of catalytic cracking feed, increasing the cracking depth and achieving the purposes of improving the product distribution of catalytic devices and increasing the target product yield.

(3) The invention also provides a preparation method, the heavy oil emulsion prepared by the method can keep a stable water-in-oil type emulsion state under the process condition of a raw material feeding unit before catalytic cracking reaction, and after entering a catalytic cracking reactor and finally contacting with a high-temperature catalyst, the emulsion is subjected to micro-explosion to form secondary atomization, so that the dispersibility and the atomization degree of catalytic cracking feeding are improved, the cracking depth is increased, and the purposes of improving the product distribution of a catalytic device and increasing the yield of target products are achieved.

(4) The invention also provides application thereof, and the emulsion preparation and the catalytic cracking industry calibration test are carried out on a 60 ten thousand ton/year industrial device, under the conditions of the reaction temperature of 515 ℃, the regeneration temperature of 690 ℃ and the raw material preheating temperature of 230 ℃, after the catalytic raw material is subjected to emulsification pretreatment by the inorganic monodisperse porous membrane, when the proportion of water to the catalytic raw material is 2%, the yield of light oil is improved by 1.70 percent, the total liquid yield is increased by 2.57 percent, the yield of slurry oil is reduced by 1.51 percent, and the yield of coke is reduced by 0.79 percent.

Detailed Description

The present invention will be further described with reference to the following examples.

The raw oil used in the emulsification test is FCC feedstock in a certain refinery, and the analysis of the properties is shown in table 1.

TABLE 1 Properties of the stock oils

The adopted emulsifier is a composite emulsifier, and the emulsifier is prepared from polyoxyethylene sorbitan fatty acid ester, triethanolamine and ethanol according to the mass ratio of 35: 35: 30: 5. The physicochemical properties of the complex emulsifier are shown in Table 2.

TABLE 2 physicochemical Properties of the Complex emulsifiers