CN107267211A - The processing method and system of a kind of inferior feedstock oil - Google Patents

Abstract

The invention discloses a kind of processing method of inferior feedstock oil and system, this method includes：A, the fluid bed that hydrogen-containing gas and inferior feedstock oil are sent into fluid bed riser reactor, which face, to contact with the first catalytic cracking catalyst in hydrogen adsorption zone (I) and carries out facing hydrogen adsorption reaction, obtains facing hydrogen adsorbed product；B, gained in step a faced into hydrogen adsorbed product send into and contacted in the riser cracking area (II) of the fluid bed riser reactor with the second catalytic cracking catalyst and carry out catalytic cracking reaction, obtain catalytic cracking oil gas.Inferior feedstock oil conversion ratio can be increased substantially and reduce dry gas and coke yield by being processed inferior feedstock oil using the inventive method on present system, so as to realize the clean and efficient utilization of inferior feedstock oil.

Description

Method and system for processing inferior raw material oil

technical field

The invention relates to a processing method and system for inferior raw material oil.

Background technique

With the shortage of petroleum resources and the increasing demand for high-quality gasoline, diesel and low-carbon olefins, the processing technology of inferior raw material oils such as coal liquefied oil, oil sand oil, and inferior and heavy petroleum products has attracted more and more attention. Inferior raw material oil, coal liquefied oil, oil sand oil, etc., are similar to natural petroleum, but contain more unsaturated hydrocarbons than natural petroleum, and contain non-hydrocarbon organic compounds such as nitrogen, sulfur and oxygen, which not only affect their secondary processing use, but also affect the color and stability of gasoline and diesel products, with high sulfur and nitrogen content. At present, except for a small amount of production of chemicals, inferior raw material oil is mostly sold as light fuel oil without secondary processing. Therefore, it is necessary to develop more technologies for efficient utilization of inferior raw material oil.

Due to the high content of nitrogen, sulfur, oxygen and other heteroatom compounds in inferior feedstock oil, especially the mass fraction of nitrogen is generally 1% to 3%, it cannot be directly used as catalytic cracking raw material for lightening inferior feedstock oil, mainly because nitrogen Compounds, especially basic nitrogen compounds, can interact with the acidic center of the catalyst to reduce the activity and selectivity of the catalyst during the catalytic cracking reaction, which is manifested in the increase of coke formation rate, increase of oil slurry and decrease of light oil yield in product distribution. ARCO pointed out that most catalytic cracking units can tolerate 2000μg/g total nitrogen and 1000μg/g base nitrogen. By adopting nitrogen-resistant cracking catalysts with high acid center density and rare earth molecular sieves, such as RHZ-200, LC-7, CCC-1, RHZ-300, or using acidic additives as nitrogen capture agents, catalytic cracking units can only process nitrogen Feed with content below 3000μg/g. In addition, low-quality feedstock oils have high colloid and olefin content. In the catalytic cracking process, one-third of the colloids will generate coke, while olefins are more active, and the two are easily adsorbed on the catalyst to cover the active center. Although colloid gasification requires a higher temperature, the higher the reaction temperature, the easier it is to generate coke.

Based on the above factors, low-quality raw oil generally needs to be upgraded by hydrotreating to remove impurities such as oxygen, nitrogen, and sulfur, and then processed into various oil products in the refinery according to the conventional refining process. U.S. Patent US 4342641 discloses a method for processing inferior raw material oil. Firstly, the whole distillate inferior raw material oil is subjected to hydrotreating, and the obtained fraction lower than 249°C is directly used as jet fuel, and the obtained fraction greater than 249°C is then subjected to hydrocracking , to produce jet fuel; the hydrotreating is carried out in two steps, first pre-refined with a catalyst with low Ni-Mo content, and then further refined with a catalyst with high Ni-Mo content. This method has many hydrogenation processes, high hydrogen consumption, high operating costs and high construction investment. Chinese patents CN 1067089A, CN 102453546A and CN 102465036A all disclose a processing method of hydrogenation fractionation of inferior feedstock oil, and catalytic cracking of hydrogenated heavy oil. Hydrogenated oil, hydrogenated oil is separated into hydrogenated heavy oil and light products, hydrogenated heavy oil is subjected to catalytic cracking to obtain dry gas, liquefied gas, gasoline, diesel and catalytic heavy oil, diesel and heavy cycle oil can be returned to the hydrotreating step It’s just that the hydrogenated heavy oil of inferior raw material oil of Chinese patent CN 102465036A adopts two riser reactors to carry out the catalytic cracking reaction, and the hydrogenated oil produced by CN 102453546A enters the catalytic cracking unit together with the optional vacuum gas oil. In a word, the processing method of hydrorefining inferior feedstock oil and refining heavy oil as raw material of existing catalytic cracking technology can convert inferior feedstock oil into light products.

Hydroprocessing of inferior raw material oil has the advantages of simple operation, high yield of target products, good product quality and no discharge of three wastes, etc. It is an environmentally friendly processing technology in the 21st century. However, non-hydrocarbon compound impurities in inferior raw material oil are harmful substances in hydroprocessing and are the object to be removed or transformed, but they themselves are useful chemical raw materials, so extraction and utilization should be considered; in addition, if inferior raw material oil A higher oxygen content will affect the life and efficiency of the hydrogenation catalyst. Hydrogenation technology is currently only achieved by the Australian SPP company, which has reached the industrial trial stage, and produces ultra-low sulfur light fuel oil through hydrorefining.

Non-hydrogenation treatment mainly adopts acid-base refining, such as patent Chinese patent CN 101967389A, acid-base refining will not only produce a large amount of acid residue that is difficult to handle, pollute the environment, and the yield of refined oil is low; although some researchers have explored the use of single solvent in recent years Or multi-solvent extraction and refining method, such as the patent Chinese patent CN CN1746265A, but there are still problems such as large solvent consumption and high energy consumption. With the improvement of environmental protection requirements, the emission standards for light fuel oil combustion exhaust at home and abroad are continuously increasing, and the restrictions on the sulfur, nitrogen and aromatic content of light fuel oil for vehicles are lower, so it is very easy to use non-hydrogenation treatment. difficult to meet the requirements.

Therefore, in order to efficiently utilize low-quality feedstock oil resources and meet the growing demand for light fuel oil, it is necessary to develop a method for efficiently converting low-quality feedstock oil into a large amount of light and clean light fuel oil.

Contents of the invention

The purpose of the present invention is to provide a method and system for processing inferior raw material oil. Using this method to process inferior raw material oil can greatly improve the conversion rate of inferior raw material oil and reduce the yield of dry gas and coke, so as to realize the processing of inferior raw material oil. Clean and efficient utilization of raw oil.

In order to achieve the above object, the present invention provides a method for processing inferior raw material oil, the method comprising: a, sending hydrogen-containing gas and inferior raw material oil into the fluidized bed hydrogen adsorption zone of the fluidized bed riser reactor and The first catalytic cracking catalyst is contacted and carried out a hydrogen adsorption reaction to obtain a hydrogen adsorption product; b, the hydrogen adsorption product obtained in step a is sent to the riser cracking zone of the fluidized bed riser reactor to be combined with the second The catalytic cracking catalyst is contacted and undergoes a catalytic cracking reaction to obtain catalytic cracking oil and gas.

Preferably, the method further includes: sending the catalytic cracked oil and gas obtained in step b to a fractionation device for fractionation treatment to obtain a catalytic cracking product including rich gas; directly sending the obtained rich gas to an absorption stabilization device without passing through a rich gas compressor Absorption stabilization treatment.

Preferably, the method further includes: in step b, carrying out the catalytic cracking reaction together with the conventional catalytic cracking feedstock oil and the hydrogen adsorption product; wherein, the conventional catalytic cracking feedstock oil is selected from wax oil, normal At least one of pressed residue oil and vacuum wax oil.

Preferably, the hydrogen-containing gas includes hydrogen and/or dry gas, and the inferior raw material oil is selected from shale oil, coal liquefied oil, oil sands oil, coker wax oil, residual oil, hydrogenated residual oil and deasphalted at least one of the oils.

Preferably, the composition of the first catalytic cracking catalyst and the second catalytic cracking catalyst is the same, including 1-50% by weight of zeolite, 5-99% by weight of inorganic oxide and 0-70% by weight of clay.

Preferably, the zeolite includes medium-pore zeolite and/or large-pore zeolite, and the medium-pore zeolite is selected from ZSM-5 zeolite, ZSM-11 zeolite, ZSM-12 zeolite, ZSM-23 zeolite, ZSM-35 zeolite, At least one of ZSM-38 zeolite, ZSM-48 zeolite and ZRP zeolite, the large-pore zeolite is at least one selected from rare earth Y-type zeolite, rare-earth hydrogen Y-type zeolite, high-silicon Y-type zeolite and ultra-stable Y-type zeolite One; the inorganic oxide is silicon oxide and/or aluminum oxide; the clay is selected from silicon dioxide, kaolin, halloysite, montmorillonite, diatomaceous earth, halloysite, saponite, rector At least one of soil, sepiolite, attapulgite, hydrotalcite and bentonite.

Preferably, said first FCC catalyst is at least one of supplemented fresh FCC catalyst, cooled regenerated FCC catalyst, cooled semi-regenerated FCC catalyst and cooled spent FCC catalyst, said second The catalytic cracking catalyst is a regenerated catalytic cracking catalyst; the temperature of the first catalytic cracking catalyst is 200-500°C, and the temperature of the second catalytic cracking catalyst is 580-680°C.

Preferably, the conditions of the hydrogen adsorption reaction include: the temperature is 200-450°C, the pressure is 0.5-5.0 MPa, the adsorption time is 1-90 seconds, the weight ratio of agent to oil is (0.5-5):1, hydrogen The oil volume ratio is 100-1000; the conditions of the catalytic cracking reaction include: the temperature is 460-540 ° C, the pressure is 0.5-5.0 MPa, the oil and gas residence time is 0.5 seconds-15 seconds, and the agent-oil weight ratio is (5- 30): 1.

Preferably, the method also includes: sending a cooling medium into the hydrogen adsorption zone of the fluidized bed for temperature control; the cooling medium is selected from cold hydrogen, water, gasoline, diesel oil, recycled oil and molten salt at least one.

The present invention also provides a processing system for low-quality raw oil, wherein the processing system includes a fluidized bed riser reactor provided with a fluidized bed section and a riser section, and a fluidized bed is formed in the fluidized bed section. Hydrogen adsorption area, a riser cracking area is formed in the riser section; the fluidized bed hydrogen adsorption area is connected in series with the riser cracking area and fluidized, and the fluidized bed section is provided with a hydrogen-containing gas inlet, inferior raw material An oil inlet and a first catalytic cracking catalyst inlet, the riser section is provided with a second catalytic cracking catalyst inlet, a catalytic cracking oil gas outlet and a catalytic cracking catalyst outlet, with or without a conventional catalytic cracking raw material oil inlet.

Preferably, the processing system further includes a fractionation device and an absorption stabilization device, the oil gas inlet of the fractionation device is in fluid communication with the catalytic cracking oil gas outlet, and the rich gas outlet of the fractionation device is connected to the rich gas outlet of the absorption stabilization device. The inlet is in fluid communication.

Preferably, the processing system further includes a regenerator, the regenerator is provided with a regenerator catalyst outlet and a regenerator catalyst inlet, the regenerator catalyst outlet is connected to the first catalytic cracking catalyst inlet and the second catalytic cracking catalyst inlet In communication, the catalyst inlet of the regenerator communicates with the outlet of the catalytic cracking catalyst.

Preferably, the catalyst outlet of the regenerator communicates with the inlet of the first catalytic cracking catalyst through a heat extractor.

Preferably, the riser section is an ascending riser reactor, the fluidized bed section is located below the riser section, and the first catalytic cracking catalyst inlet is located at the lower part of the fluidized bed section, and the second The catalytic cracking catalyst inlet is located at the lower part of the riser section, and the catalytic cracking catalyst outlet is located at the upper part of the riser section; or, the riser section is a descending riser reactor, and the fluidized bed section is located at the top of the riser section. Above, and the first catalytic cracking catalyst inlet is located at the upper part of the fluidized bed section, the second catalytic cracking catalyst inlet is located at the upper part of the riser section, and the catalytic cracking catalyst outlet is located at the lower part of the riser section .

Preferably, the diameter of the fluidized bed hydrogen adsorption zone is 0.5-5 times the diameter of the riser cracking zone, and the length of the fluidized bed hydrogen adsorption zone is 1-30% of the length of the riser cracking zone .

Preferably, the fluidized bed section is provided with a cooling medium inlet, and the cooling medium inlet is in direct fluid communication with the hydrogen adsorption zone of the fluidized bed or with a heat extraction system arranged in the hydrogen adsorption zone of the fluidized bed. fluid communication.

Compared with the prior art, the present invention has the following technical effects:

(1) Inferior raw material oil can be directly processed without refining treatment, the processing flow of inferior raw material oil is short, the hydrogen consumption is low, and long-term continuous production can be realized;

(2) The present invention adopts "one device and two reverses" to process low-quality raw material oil, that is, the first catalytic cracking catalyst and the second catalytic cracking catalyst that are the same or different are loaded into a reactor, and these two catalysts are in the same reaction atmosphere. Synergistically complete the function of adsorbing impurities such as sulfides, basic nitrogen compounds, heavy metals and colloids and catalytic cracking of inferior raw material oils with inferior raw materials, and then recover the activity simultaneously in the same regeneration atmosphere;

(3) Inferior raw material oil first adsorbs and removes polar substances such as sulfides, basic nitrogen compounds, heavy metals and colloids, and then catalytically cracks. The conversion rate of inferior raw material oil is high, and the yield of dry gas and coke is low, which reduces the coke formation of the device , high yield of liquid products (liquefied gas + gasoline + diesel);

(4) Adsorption of inferior raw material oil in a hydrogen atmosphere is more conducive to the adsorption and removal of sulfur-containing, nitrogen-containing and oxygen-containing compounds in inferior raw material oil by the first catalytic cracking catalyst. The weight ratio is reduced, the adsorption time is short, and the liquid product has low sulfur and nitrogen content and good quality;

(5) The processing system is operated under the hydrogen band pressure, which correspondingly increases the pressure of the rich gas entering the absorption stabilization device, saves the rich gas compressor of the conventional FCC process, and reduces the energy consumption of the device;

(6) The fluidized bed riser reactor is more suitable for the characteristics of fast catalytic cracking reaction. Compared with fixed bed and moving bed, the reactor volume utilization rate is high, and it is more suitable for continuous operation of large-scale production, and can utilize the existing The riser reactor unit was modified.

Other features and advantages of the present invention will be described in detail in the following detailed description.

Description of drawings

The accompanying drawings are used to provide a further understanding of the present invention, and constitute a part of the description, together with the following specific embodiments, are used to explain the present invention, but do not constitute a limitation to the present invention. In the attached picture:

Fig. 1 is a schematic flow chart of the first specific embodiment including the processing method of the present invention, and also a schematic structural view of the first specific embodiment including the processing system of the present invention;

Fig. 2 is a schematic flow chart of a second specific embodiment including the processing method of the present invention, and also a schematic structural view of a second specific embodiment including the processing system of the present invention;

Fig. 3 is a schematic flowchart of a third specific embodiment including the processing method of the present invention, and is also a schematic structural view of a third specific embodiment including the processing system of the present invention.

Explanation of reference signs

I Fluidized bed hydrogen adsorption zone II Riser cracking zone 1 Hydrogen-containing pre-lift medium

2 Fluidized bed riser reactor 3 Inferior feedstock oil 4 Hydrogen-containing gas

5 Stripping steam 6 Settler 7 Pipeline

8 Fractionation unit 9 Pipeline 10 Absorption stabilization unit

11 dry gas 12 pipeline 13 regenerator

14 regeneration gas 15 flue gas 16 pipeline

17 heat extractor 18 cooling medium inlet 19 cooling medium outlet

20 pipeline 21 pipeline 22 lifting medium

23 Conventional catalytic cracking feed oil

24 Conventional catalytic cracking raw oil atomization medium 25 Liquefied gas

26 Gasoline 27 Diesel 28 Oil slurry

detailed description

Specific embodiments of the present invention will be described in detail below in conjunction with the accompanying drawings. It should be understood that the specific embodiments described here are only used to illustrate and explain the present invention, and are not intended to limit the present invention.

The present invention provides a method for processing inferior raw material oil, the method comprising: a, sending hydrogen-containing gas and inferior raw material oil into the fluidized bed hydrogen adsorption zone I of the fluidized bed riser reactor to be combined with the first catalytic cracking Catalyst contacts and carries out hydrogen adsorption reaction, obtains hydrogen adsorption product; b, the hydrogen adsorption product obtained in step a is sent into the riser cracking zone II of described fluidized bed riser reactor and the second catalytic cracking catalyst Contact and carry out catalytic cracking reaction to obtain catalytic cracking oil and gas.

The inventor of the present invention unexpectedly found through many years of research that nitrogen-containing compounds, sulfur-containing compounds and oxygen-containing compounds in inferior raw material oil can be removed by adsorption, and the catalytic cracking catalyst itself can also be used as an adsorbent; especially in In the presence of hydrogen, the adsorption time is short, which is more conducive to the adsorption and removal of sulfur-containing compounds, nitrogen-containing compounds, oxygen-containing compounds and metals in the inferior raw material oil by the first catalytic cracking catalyst, so that the conversion rate of the inferior raw material oil is high, and the liquid The product has low sulfur and nitrogen content and good quality.

According to the present invention, the method may also include: sending the catalytic cracked oil and gas obtained in step b to a fractionation device 8 for fractionation treatment to obtain catalytic cracking products including rich gas; directly sending the obtained rich gas into the absorption unit without passing through the rich gas compressor The stabilizing device 10 performs absorption stabilizing treatment. The reaction and fractionation system of the conventional catalytic cracking unit operates at a pressure of 0.1-0.25 MPa, while the absorption and stabilization unit needs to operate at a pressure above 1.1 MPa. Therefore, the conventional catalytic cracking unit must be equipped with a gas-rich compressor The rich gas is compressed and raised. The reaction system of the present invention is operated under the pressure of hydrogen (0.5-5.0MPa), which correspondingly increases the pressure of the rich gas entering the absorption and stabilization device, and can save the rich gas compressor in the conventional FCC process. Thereby reducing device energy consumption and cost input. The fractionation device obtains rich gas, diesel oil and oil slurry, and the rich gas at the top of the fractionation device (fractionation tower) can directly enter the absorption stabilization device for further product separation without being compressed by the rich gas compressor to obtain dry gas, liquefied gas and gasoline. The distillation range of gasoline or diesel can be adjusted according to actual needs, not limited to full-range gasoline or diesel.

According to the present invention, in order to increase the processing capacity of the processing method, the method may also include: in step b, performing the catalytic cracking reaction on the conventional catalytic cracking feedstock oil and the hydrogen adsorption product; wherein, the conventional catalytic cracking The cracked raw oil may be at least one selected from wax oil, atmospheric residue and vacuum gas oil. The inferior raw material oil is fed in the hydrogen adsorption zone of the fluidized bed, and the conventional catalytic cracking raw material oil is fed in the cracking zone of the riser; the inferior raw material oil after removing impurities by hydrogen adsorption and part of the first catalytic cracking catalyst Enter the riser cracking zone, and contact with the second catalytic cracking catalyst together with the conventional catalytic cracking feed oil entering the riser cracking zone, to carry out the catalytic cracking reaction.

According to the present invention, the hydrogen-containing gas is well known to those skilled in the art, and it can be used as a hydrogen source or as an inferior raw material oil transport gas. Its composition is not particularly limited in the present invention. For example, the hydrogen-containing gas can include Hydrogen and/or dry gas may also include non-hydrogen-containing media such as nitrogen and water vapor. The non-hydrogen-containing media does not contain or contain a small amount of oxygen, and the volume fraction of oxygen in the hydrogen-containing gas is not more than 1%; inferior raw material oil is As known to those skilled in the art, it can be at least one selected from shale oil, coal liquefied oil, oil sands oil, coker wax oil, residual oil, hydrogenated residual oil and deasphalted oil, and the relative density can be 0.8- 1.1, can be rich in alkanes, aromatics and some alkenes, the weight ratio of carbon and hydrogen elements can be 7-9, and the content of non-hydrocarbon organic compounds such as nitrogen, sulfur and oxygen is relatively high, and the nitrogen content can be 0.5%-5%, sulfur The content can be 0.5%-10%, and the oxygen content can be 0.5%-20%.

In the present invention, the inferior raw material oil can be sent to the reactor for reaction after being preheated, and the preheating temperature can be 150-400°C, preferably 200-350°C.

According to the present invention, the catalytic cracking catalyst is well known to those skilled in the art, the first catalytic cracking catalyst and the second catalytic cracking catalyst can be the same or different, and the activity of the catalytic cracking catalyst can be 40-70, preferably 45-60. The composition of the catalytic cracking catalyst may include: zeolite, inorganic oxides and optional clay; the specific composition and usage amount of the first catalytic cracking catalyst and the second catalytic cracking catalyst depend on the nitrogen content of inferior raw material oil and the denitrification Requirements, determined by the catalytic cracking reaction conditions, preferably, the first catalytic cracking catalyst and the second catalytic cracking catalyst have the same composition, both can include 1-50% by weight of zeolite, 5-99% by weight of inorganic oxides and 0-70% by weight clay. Wherein, the zeolite can be a medium-pore zeolite and/or an optional large-pore zeolite, and the medium-pore zeolite can account for 80-100% by weight of the total weight of the zeolite, preferably 90-100% by weight; the large-pore zeolite can account for the total weight of the zeolite. 0-20% by weight, preferably 0-10% by weight. The medium pore zeolite can be ZSM series zeolite and/or ZRP zeolite, preferably selected from ZSM-5 zeolite, ZSM-11 zeolite, ZSM-12 zeolite, ZSM-23 zeolite, ZSM-35 zeolite, ZSM-38 zeolite, ZSM- At least one of 48 zeolite and ZRP zeolite may also include other zeolites of similar structure. A more detailed description of ZSM-5 zeolite can be found in US Patent No. 3,702,886, and a more detailed description of ZRP zeolite can be found in US Patent No. 5,232,675. The large-pore zeolite can be a Y series zeolite, and can include at least one of rare earth Y zeolite (REY), rare earth hydrogen Y zeolite (REHY), ultra-stable Y zeolite (obtainable by different methods) and high silicon Y zeolite. A sort of. The inorganic oxide is generally used as a binder, which can be silicon oxide (SiO ₂ ) and/or aluminum oxide (Al ₂ O ₃ ). In terms of dry weight, silicon oxide in the inorganic oxide can account for 50-90 weight %, alumina can account for 10% by weight -50% by weight. Described clay is as substrate (being carrier), can be selected from silica, kaolin, halloysite, montmorillonite, diatomaceous earth, halloysite, saponite, rectorite, sepiolite, attapulgite , at least one of hydrotalcite and bentonite. Preferably, the above-mentioned macroporous and mesoporous zeolites, inorganic oxides and clays can be modified by using iron, cobalt, nickel and other transition metal element components. The first catalytic cracking catalyst and the second catalytic cracking catalyst are mainly in the shape of microspheres, and their diameters can be greater than 0 to 200 microns, more preferably 40-150 microns, and the apparent densities of the catalysts can be 0.4-1.9 g/cm ³ , respectively. More preferably, it is 0.8-1.5 g/cm ³ .

According to the present invention, the first catalytic cracking catalyst and the second catalytic cracking catalyst may be catalysts with different particle sizes and/or catalysts with different apparent bulk densities. The active components of catalysts with different particle sizes and/or different apparent bulk densities can also be selected from different types of zeolites, or metal and non-metal modified zeolites, catalysts with different particle sizes and/or different apparent bulk densities Catalysts can enter different riser cracking zones respectively. For example, catalysts containing small particles of high-silicon-aluminum ratio rare earth ultrastable Y-type zeolite can enter fluidized bed hydrogen adsorption zone I (as the first catalytic cracking catalyst) to increase alkali Adsorption and removal reactions of polar substances such as neutral nitrides, heavy metals and/or colloids, asphaltenes, etc. Catalysts containing large particles of ultra-stable Y-type zeolite can enter riser cracking zone II (as the second catalytic cracking catalyst) to increase catalytic cracking reactions. Catalysts with different particle sizes are stripped in the same stripper and regenerated in the same regenerator. Then the catalysts with large particles and small particles are separated, and the catalysts with small particles enter the hydrogen adsorption zone I of the fluidized bed after being cooled. Catalysts with different particle sizes can be divided between 30-40 microns, and catalysts with different apparent bulk densities can be divided between 0.6-0.7 g/cm ³ .

According to the present invention, in order to control the temperature of the hydrogen adsorption reaction and the catalytic cracking reaction, the first catalytic cracking catalyst can be supplemented fresh catalytic cracking catalyst, cooled regenerated catalytic cracking catalyst, cooled semi-regenerated catalytic cracking catalyst and cooled catalytic cracking catalyst. At least one of the pending catalytic cracking catalysts, the second catalytic cracking catalyst may be a regenerated catalytic cracking catalyst; the temperature of the first catalytic cracking catalyst may be 200-500°C, more preferably 230-480°C, the second The temperature of the second catalytic cracking catalyst can be 580-680°C. Preferably, the first catalytic cracking catalyst can be a mixture of a regenerated catalytic cracking catalyst and a fresh catalytic cracking catalyst after heat exchange, and the fresh catalytic cracking catalyst after heat exchange has a good adsorption effect on nitrogen, especially basic nitrogen, and desorbs The nitrogen rate is high; and the activity of the fresh catalytic cracking catalyst after adsorption and denitrification is reduced, and the coke generation is low in the catalytic cracking process.

According to the present invention, the hydrogen adsorption reaction and catalytic cracking reaction are well known to those skilled in the art. For example, the conditions of the hydrogen adsorption reaction may include: a temperature of 200-450°C, preferably 250-400°C, and a pressure of 0.5-5.0 MPa, preferably 1.0-4.0 MPa, adsorption time is 1-90 seconds, preferably 2-60 seconds, agent-oil weight ratio is (0.5-5.0): 1, preferably (1-4): 1. The volume ratio of hydrogen to oil is 100-1000, preferably 300-800; the conditions of the catalytic cracking reaction may include: a temperature of 460-540°C, preferably 480-530°C, and a pressure of 0.5-5.0 MPa, preferably 1.0-4.0 MPa, the oil-gas residence time is 0.5-15 seconds, preferably 1.0-10 seconds, and the agent-oil weight ratio is (5-30):1, preferably (6-30):1. The apparent average linear velocity of the oil and gas in the hydrogen adsorption zone I of the fluidized bed can be 0.5-8.0 m/s, and the apparent average linear velocity of the oil and gas in the riser cracking zone II can be 10-60 m/s ; Preferably, the apparent average linear velocity of the oil and gas in the hydrogen adsorption zone I of the fluidized bed is 8-52 m/s lower than the apparent average linear velocity of the oil and gas in the riser cracking zone II, and the second A catalytic cracking catalyst is in a fluidized state, preferably in a turbulent fluidized state.

According to the present invention, the division of the fluidized bed hydrogen adsorption zone and the riser cracking zone can be different from the reactor, and cooling medium can also be injected at the bottom or top of the reactor. By introducing the cooling medium, the hydrogen adsorption and catalytic cracking process Organic combination, so as to realize the hydrogen catalytic cracking of inferior raw material oil, and improve the conversion ability of inferior raw material oil. Therefore the method may also include: sending a cooling medium into the hydrogen adsorption zone I of the fluidized bed for temperature control; At least one: the cooling medium can be directly injected into the reactor, or the catalyst can exchange heat with the cooling medium by arranging heat extraction coils in the reactor, thereby controlling the temperature of the hydrogen adsorption zone of the fluidized bed.

The present invention also provides a processing system for low-quality raw oil, wherein the processing system includes a fluidized bed riser reactor provided with a fluidized bed section and a riser section, and a fluidized bed is formed in the fluidized bed section. Hydrogen adsorption zone I, a riser cracking zone II is formed in the riser section; the fluidized bed hydrogen adsorption zone I is connected in series with the riser cracking zone II, and the fluidized bed section is provided with hydrogen-containing gas Inlet, low-quality raw oil inlet and first catalytic cracking catalyst inlet, the riser section is provided with a second catalytic cracking catalyst inlet, catalytic cracking oil gas outlet and catalytic cracking catalyst outlet, with or without a conventional catalytic cracking raw material oil inlet. Wherein, the catalytic cracking oil gas outlet and the catalytic cracking catalyst outlet may be the same or different.

According to a specific embodiment of the present invention, the processing system may also include a fractionation device 8 and an absorption stabilization device 10, the oil and gas inlet of the fractionation device 8 may be in fluid communication with the catalytic cracking oil and gas outlet, and the fractionation device 8 The rich gas outlet can be in fluid communication with the rich gas inlet of the absorption stabilization device 10 . The existing conventional catalytic cracking unit reaction and fractionation unit is generally operated at a pressure of 0.1-0.25MPa, while the absorption stabilization unit needs to be operated at a pressure above 1.1MPa, so the conventional catalytic cracking unit must be equipped with a gas-rich compressor The rich gas is compressed and raised, and the processing system of the present invention operates under hydrogen pressure (0.5-5.0MPa), which correspondingly increases the pressure of the rich gas entering the absorption and stabilization device, which can save the rich gas compressor in the conventional FCC process, thereby reducing Device energy consumption.

According to the present invention, in order to facilitate the regeneration of the catalyst, the processing system can also include a regenerator 13, the regenerator 13 can be provided with a regenerator catalyst outlet and a regenerator catalyst inlet, and the regenerator catalyst outlet (this outlet can be One, or two or more) can communicate with the first catalytic cracking catalyst inlet and the second catalytic cracking catalyst inlet, and the regenerator catalyst inlet can communicate with the catalytic cracking catalyst outlet. The regeneration temperature of the regenerator is generally 550-700°C, preferably 600-650°C, and the regenerated catalytic cracking catalyst is recycled. During the regeneration process, the regeneration gas can be at least A sort of. The heat exchange of the regenerated catalyst can be carried out by methods known to those skilled in the art, so as to control the amount of coke produced and the contact temperature of the oil agent.

According to a specific embodiment of the present invention, the riser section may be an ascending riser reactor, the fluidized bed section may be located below the riser section, and the first catalytic cracking catalyst inlet may be located in the fluidized bed The lower part of the riser section, the second catalytic cracking catalyst inlet can be located at the lower part of the riser section, and the catalytic cracking catalyst outlet can be located at the upper part of the riser section; or, the riser section can be a descending riser reactor , the fluidized bed section can be located above the riser section, and the first catalytic cracking catalyst inlet can be located in the upper part of the fluidized bed section, and the second catalytic cracking catalyst inlet can be located in the upper part of the riser section , the catalytic cracking catalyst outlet may be located at the lower part of the riser section.

In the present invention, the inferior raw material oil enters the fluidized bed hydrogen adsorption area of the reactor, and according to the setting of the fluidized bed hydrogen adsorption area, the inferior raw material oil can adopt the lower feed or the upper feed; if the lower feed , the inferior raw material oil enters the hydrogen adsorption zone of the fluidized bed from the bottom of the ascending fluidized bed riser reactor, and flows upward along with the hydrogen-containing gas; The top of the riser reactor of the fluidized bed enters the hydrogen adsorption zone of the fluidized bed, and the inferior raw material oil flows from top to bottom along with the hydrogen-containing gas; the inferior raw material oil enters the hydrogen adsorption zone of the fluidized bed, and is first Impurities such as basic nitrides are adsorbed and removed from the first catalytic cracking catalyst with the nitrogen adsorption function.

According to the present invention, the fluidized bed section and the riser section are well known to those skilled in the art. The fluidized bed is adjacent to the hydrogen adsorption zone, the reaction temperature is relatively low, a certain amount of catalyst storage is maintained, and the apparent average linear velocity of oil and gas is generally 0.5-8.0 The superficial linear velocity of oil and gas in the riser cracking zone is generally 10-60 m/s. The diameter of the fluidized bed hydrogen adsorption zone I can be 0.5-5 times the diameter of the riser cracking zone II, preferably 1-4 times, more preferably 1.0-2.0 times, the fluidized bed hydrogen adsorption zone The length of zone I may be 1-30%, preferably 10-25%, more preferably 10-20% of the length of riser cracking zone II. The fluidized bed hydrogen adsorption zone and riser cracking zone refer to the space in the reactor where hydrogen adsorption reaction and catalytic cracking reaction can be carried out, and the reactor itself is not included. If the diameter of the reactor is expanded at the end of the cracking zone of the riser, the conversion of sulfides and olefins in gasoline, the cracking product of inferior raw material oil, can be enhanced. After the catalytic cracking reaction is completed, a cooling medium can be injected into the upper part or the outlet of the riser as a terminator according to the needs of the termination reaction. The cooling medium can be water, gasoline or diesel oil, etc.

According to the present invention, because the temperature of the hydrogen adsorption reaction and the catalytic cracking reaction is different, the catalyst outlet of the regenerator can be communicated with the inlet of the first catalytic cracking catalyst through the heat collector 17, so that the regenerated catalyst is cooled and then Enter the hydrogen adsorption zone of the fluidized bed.

A specific embodiment, as shown in Figures 1-3, the fluidized bed section is provided with a cooling medium inlet, the cooling medium inlet is in direct fluid communication with the hydrogen adsorption zone I of the fluidized bed or with the The fluidized bed is in fluid communication with the heat extractor 17 in the hydrogen adsorption zone I.

The present invention will be further described through specific embodiments below, but the present invention is not limited thereby.

As shown in Figure 1, Figure 1 is a schematic process flow diagram of a first specific embodiment of the present invention. In this specific embodiment, a composite reactor composed of a fluidized bed section and a riser section is used, and the riser section is an uplink Type riser reactor, the enlarged fluidized bed hydrogen adsorption zone I is in the lower part of the riser section, and the low-quality raw material oil enters the fluidized bed hydrogen adsorption zone I in the fluidized bed riser reactor with lower feed, and is adsorbed and desorbed. After nitrogen, it goes up into riser cracking zone II for catalytic cracking reaction. Its technological process is as follows:

Inferior raw oil adopts a fluidized bed riser reactor composed of a fluidized bed section and a riser section, which is first adsorbed and denitrified and then catalytically cracked. Afterwards, the first catalytic cracking catalyst cooled by the external heat extractor 17; the inferior raw material oil 3 enters the hydrogen adsorption zone I of the fluidized bed from the bottom of the enlarged diameter of the reactor 2, and along with the pre-lifting medium 1 containing hydrogen and the The gas 4 goes up together, and performs reaction adsorption on the first catalytic cracking catalyst to remove impurities such as basic nitrides, sulfides, colloids and/or heavy metals; the hydrogen-adsorbed products then go up into the riser cracking of reactor 2 Zone II, contact with the high-temperature and high-activity second catalytic cracking catalyst from the regenerator 13 through the pipeline 21 for catalytic cracking reaction; the generated oil gas and catalyst (part of the first catalytic cracking catalyst and the second catalytic cracking catalyst) enter the settler 6 for sedimentation and separation, the separated oil and gas enters the fractionation unit 8 to obtain diesel oil 27 and oil slurry 28, and the rich gas at the top of the fractionation unit is not compressed by the rich gas compressor and directly enters the absorption stabilization unit 10 for further product separation to obtain dry gas 11, For products such as liquefied gas 25 and gasoline 26, the dry gas 11 is selected to be partly circulated back to the hydrogen adsorption zone of the fluidized bed as the hydrogen-containing gas or pre-lifting medium according to the needs, and the oil slurry 28 is selected to be re-refined or not re-refined according to the needs; the separated After the catalyst is stripped by the stripping steam 5 to remove the adsorbed oil and gas, it is sent to the regenerator 13 for regeneration in the regeneration gas (air) 14, the regeneration temperature is 600-680°C, and the regenerated regenerant is recycled.

As shown in Figure 2, Figure 2 is a schematic diagram of the process flow of the second specific embodiment of the present invention. In this specific embodiment, conventional catalytic cracking feedstock oil is blended with low-quality feedstock oil, and its process flow is the same as that of specific embodiment 1. The schematic diagram of the flow chart is basically the same, except that a stream of conventional raw material oil and its atomization medium are injected into the riser cracking zone II through pipelines 23 and 24 respectively in this embodiment, and the specific position is that the second catalytic cracking catalyst enters the fluidized bed riser for reaction. Above the regeneration pipeline 21 of the device, it is blended with inferior raw material oil. In this specific embodiment, the apparent average linear velocity of the oil and gas in the hydrogen adsorption zone I of the fluidized bed is 8-25 m/s lower than the apparent average linear velocity of the oil and gas in the riser cracking zone II, maintaining The hydrogen adsorption zone of the fluidized bed is in a turbulent fluidized state.

As shown in Figure 3, Figure 3 is a schematic process flow diagram of the third embodiment of the present invention. In this specific embodiment, the reactor is a down-flow fluidized bed riser reactor, and the expanded fluidized bed Hydrogen adsorption zone I is in the upper part of the riser adsorption zone II, and the inferior raw material oil is fed into the fluidized bed hydrogen adsorption zone I in the reactor, and then catalytic cracking after adsorption and denitrification in the hydrogen atmosphere , descending into riser cracking zone II for catalytic cracking reaction. In addition, unlike the heat extractor arranged outside the reactor in the first embodiment, the heat extractor is arranged in the fluidized bed section in this specific embodiment. Its technological process is as follows:

The inferior raw material oil adopts the down-flowing fluidized bed riser reactor 2 to first absorb nitrogen and then catalytic cracking, and the upper part of the reactor 2 expands into a fluidized bed hydrogen adsorption zone I; 4. The upper feed is used, and the inferior raw material oil 3 enters the hydrogen adsorption zone I of the fluidized bed from the enlarged top of the reactor 2, and reacts on the first catalytic cracking catalyst from the pipeline 20 as the hydrogen-containing gas flows downward. Adsorption removes impurities such as basic nitrides, sulfides, colloids, and/or heavy metals, and uses heat extractor 17 to extract heat to control temperature; the hydrogen-adsorbed product then descends into the riser of the reactor 2 for cracking Zone II, contact with the high-temperature and high-activity second catalytic cracking catalyst from the pipeline 21 of the regenerator 13 to undergo a catalytic cracking reaction; the generated oil gas and catalyst enter the settler 6 for sedimentation and separation, and the separated oil gas enters the fractionation device 8 to obtain Diesel oil 27, oil slurry 28, the rich gas at the top of the fractionation tower directly enters the absorption and stabilization device 10 for further product separation without being compressed by the rich gas compressor, and obtains products such as dry gas 11, liquefied gas 25 and gasoline 26, and the dry gas 11 is selected according to needs Partially circulated back to the hydrogen adsorption zone I of the fluidized bed as the hydrogen-containing gas or pre-lifting medium, and the oil slurry 28 can be re-refined or not re-refined according to the needs; the separated catalyst is stripped by the stripping steam 5 to remove the adsorbed oil and gas , sent to the regenerator 13 to regenerate in the regenerating gas (air) 14, the regenerating temperature is 600-680°C, and the regenerating agent after regeneration is recycled.

The present invention will be further described below by way of examples, but the present invention is not limited thereto.

The product detection methods of Examples and Comparative Examples are: the reaction product is carried by N into a liquid collection bottle at -10°C for gas _- liquid separation, and the gas product collection is completed by Agilent 6890GC (TCD detector) on-line analysis; liquid product collection After off-line weighing, simulated distillation and gasoline monomer hydrocarbon analysis were carried out respectively (tested by RIPP81-90 test method). The cut points of gasoline and diesel fractions were 221°C and 343°C respectively; Coke analysis is carried out on the 2000 carbon and sulfur analyzer (using the RIPP106-90 test method for testing), all product masses are added to calculate the material balance, and the sulfur and nitrogen content in hydrogen adsorption products and gasoline adopts RIPP 62-90 test method and RIPP 63- 90 test method for determination, the metal content is determined by RIPP 124-90 test method.

The inferior raw material oils used in the examples and comparative examples are shale oil (A), residual oil (B) and vacuum gas oil C, and their properties are shown in Table 1.

The first catalytic cracking catalyst used in the embodiment is identical to the second catalytic cracking catalyst, and its preparation method is briefly described as follows:

1) Dissolve 20g NH ₄ Cl in 1000g water, add 100g (dry basis) crystallization product DASY zeolite (produced by Qilu Petrochemical Company Catalyst Factory) to this solution, the unit cell size is 2.445-2.448nm, the rare earth content (in RE ₂ O ₃ ) = 2.0 wt%), exchanged at 90°C for 0.5h, and filtered to obtain a filter cake; 4.0g H ₃ PO ₄ (concentration 85%) and 5.4g Co(NO ₃ ) ₂ ·6H ₂ O were dissolved in 90g water , mixed with the filter cake, impregnated, dried, and then roasted at 550°C for 2 hours to obtain a large-pore zeolite containing phosphorus and cobalt. The chemical element composition is: 0.1Na ₂ O·5.1Al ₂ O ₃ ·2.4P ₂ O _{5 ·} 1.5Co2O3 _{· 3.8RE2O3 · 88.1SiO2} .

2), beat 75.4Kg halloysite (industrial product of Suzhou China Clay Company, solid content 71.6m%) with 250Kg decationized water, then add 54.8Kg pseudo-boehmite (industrial product of Shandong Aluminum Factory, solid content 63m%) , adjust its pH to 2-4 with hydrochloric acid, stir evenly, leave it to age at 60-70°C for 1 hour, keep the pH at 2-4, lower the temperature below 60°C, add 41.5Kg of aluminum sol (Qilu Petrochemical The company's catalyst factory product, Al ₂ O ₃ content is 21.7m%), stirred for 40 minutes to obtain a mixed slurry.

The phosphorus- and cobalt-containing large-pore zeolite (33.8Kg on a dry basis) prepared in step 1) and the mesoporous ZRP-1 zeolite with MFI structure (industrial product of Qilu Petrochemical Company Catalyst Factory, SiO ₂ /Al ₂ O ₃ =30, dry base is 3.0Kg) into the mixed slurry obtained in step 2), stir evenly, and add appropriate amount of special adhesive, structural aid and pore-forming agent, mix and put it in the bonding machine, add appropriate amount of water, and fully stir Uniform, placed in the air for 4 hours, spray-dried to shape, dried in a drying oven at 120°C for 3 hours, washed with ammonium dihydrogen phosphate solution (phosphorus content: 1m%), washed to remove free Na ⁺ , washed to remove free Na ⁺ , and dry again to obtain the catalyst as CAT-3. The composition of the catalyst is 4.1% by weight of MFI structure mesoporous zeolite, 20.6% by weight of DASY zeolite containing phosphorus and cobalt, 29.4% by weight of pseudo-boehmite, 5.5% by weight of alumina sol and the balance of kaolin. Its properties are listed in Table 2.

Example 1

This embodiment is tested according to the flow process of Fig. 1, and shale oil A is used as the raw material of catalytic cracking, and test is carried out on the small-scale continuous regenerative fluidized bed riser reactor, and shale oil A is fed under, and the expansion diameter of reactor bottom is The internal diameter of the riser cracking zone II is five times that of the fluidized bed hydrogen adsorption zone I, and the length of the hydrogen adsorption zone I is 14% of the length of the riser cracking zone II. Adsorption zone I introduces the cold regenerated catalytic cracking agent from outside as the first catalytic cracking catalyst, and the dry gas with a hydrogen gas fraction of 85% (the rest is methane, ethane and ethylene, etc.) flows from bottom to top as hydrogen-containing gas, and the The pipe cracking zone is transported into the high-temperature heat regenerated catalytic cracking agent as the second catalytic cracking catalyst; the CAT-3 catalyst is used as the first catalytic cracking catalyst and the second catalytic cracking catalyst at the same time, and the microreaction activity (MAT) of the CAT-3 balancer is 65. After being preheated at 260°C, the shale oil enters the bottom of the adsorption zone I where the diameter of the fluidized bed riser reactor expands. Under the reaction pressure of 4.2 MPa, the volume ratio of H ₂ /shale oil is 500. Downward and upward flow, under the conditions of adsorption temperature 300°C, weight ratio of the first catalytic cracking catalyst to shale oil A of 4.8, and adsorption time of 12 seconds, hydrogen adsorption reaction is carried out to remove basic nitrides, sulfides and heavy metals, etc. Impurities; the hydrogen-adsorbed product goes up into the riser cracking zone, and catalytic cracking reaction occurs together at 500°C, the weight ratio of the second catalytic cracking catalyst to the hydrogen-adsorbed product is 6.4, and the reaction time is 3.5 seconds; the generated oil gas enters the The fractionation unit obtains diesel oil and oil slurry. The rich gas at the top of the fractionation unit is not compressed by the rich gas compressor and directly enters the absorption stabilization unit for further product separation to obtain dry gas, liquefied gas, gasoline and other products. The oil slurry recovery ratio is 0.1. After reacting for a certain period of time, the raw catalytic cracking catalyst is stripped with N ₂ to remove the oil gas adsorbed inside it, and then sent to the regenerator using air as the regeneration gas, and is contacted with the raw catalytic cracking catalyst at a regeneration temperature of 600-680°C. Regeneration; the regenerant after regeneration is recycled. The operating conditions and product distribution are listed in Table 3.

It can be seen from Table 3 that the shale oil A was subjected to hydrogen adsorption first and then catalytic cracking, its adsorption desulfurization rate was 82% by weight, the denitrification rate was 87% by weight, and the demetallization rate was 62.0% by weight; Catalytic cracking, conversion (100%-diesel yield-oil slurry yield) is 68.1% by weight, oil slurry yield is 5.5% by weight, dry gas yield is 2.3% by weight, coke yield is 7.8% by weight, liquid product yield (Liquefied gas yield+gasoline yield+diesel yield) up to 84.4% by weight, of which the gasoline yield is as high as 41.8% by weight, and the propylene yield is as high as 4.9% by weight; the sulfur content of the product gasoline is 52.5ppm, and the nitrogen content is 85.2ppm.

Comparative example 1

This comparative example uses shale oil A as a raw material, with CAT-3 as the first catalytic cracking catalyst and the second catalytic cracking catalyst, and the balancer MAT is 65, carried out on the small-scale fluidized bed riser catalytic cracking device of embodiment 1 The test is different from Example 1: the hydrogen-containing gas is replaced by hydrogen-free water vapor, the reactor pressure is 0.22MPa, and no cooling medium is injected, while shale oil A and water vapor are directly injected into the fluidized bed for reaction The reaction zone of the reactor, that is, the shale oil A directly performs the catalytic cracking reaction on the second catalytic cracking catalyst without adsorption; after the reaction, the rich gas at the top of the fractionation unit is compressed and raised to 1.2-1.6MPa by the rich gas compressor and then enters The absorption stabilization device further separates the product; the heavy oil refining ratio is 0.3. The operating conditions and product distribution are listed in Table 3.

It can be seen from Table 3 that shale oil A directly undergoes non-hydrocatalytic cracking reaction without adsorption, the conversion rate is 66.6 wt%, the oil slurry yield is 6.5 wt%, the dry gas yield is 3.0 wt%, and the coke yield is 9.8 wt%. %, the liquid product yield is 80.7% by weight, wherein the gasoline yield is 39.3% by weight, and the propylene yield is 4.4% by weight; the product gasoline has a sulfur content of 291.5ppm and a nitrogen content of 458.6ppm.

As can be seen from the data in Table 3, the shale oil A is processed by the method of the present invention, the shale oil conversion capacity is high, the refining ratio is low, the conversion rate is increased by 1.5 percentage points, and the oil slurry yield is 1.0 percentage points lower , while the yield of dry gas and coke is low, the yield of dry gas + coke is 2.7 percentage points lower, and the yield of liquid products is increased by 3.7 percentage points; the sulfur content of product gasoline is reduced by 249.0ppm, and the nitrogen content is reduced by 373.4ppm.

Example 2

Embodiment 2 is tested according to the equipment and flow process of Fig. 2, uses residual oil B and vacuum wax oil C in table 1 as the raw material of catalytic cracking, and residual oil B and vacuum wax oil C partition feeding, promptly residual oil B is in The fluidized bed hydrogen adsorption zone I feeds and the vacuum wax oil C feeds in the riser cracking zone II; the diameter expansion of the fluidized bed at the bottom of the reactor becomes the turbulent fluidized bed hydrogen adsorption zone (fluidized bed hydrogen adsorption zone The internal diameter of the zone is 3 times of the internal diameter of the cracking zone of the riser, and the length of the hydrogen adsorption zone of the fluidized bed is 10% of the cracking zone length of the riser), and the cooling first catalytic cracking catalyst of the external heat extraction is introduced , the dry gas with a volume fraction of 80% (the rest is methane, ethane and ethylene, etc.) is used as the hydrogen-containing gas; the lower part of the riser cracking zone II is transported into the high-temperature second catalytic cracking catalyst, and the riser cracking is formed in the upper part of the riser section Zone II. Residue B, which accounts for 30% by weight of the total feed, is preheated at 300°C and enters the bottom of the riser reactor in a fluidized bed with expanded diameter. Flow, under the conditions of adsorption temperature 350°C, weight ratio of the first catalyst to residual oil 3.0, pressure 3.5MPa, adsorption time 5.0 seconds, hydrogen adsorption reaction is carried out to remove impurities such as basic nitrides, sulfides and heavy metals , the apparent average linear velocity of oil and gas in the hydrogen adsorption zone I of the fluidized bed is 0.5 m/s; the residual oil and part of the first catalytic cracking catalyst go up into the cracking zone II of the riser, and the high temperature from the regenerator After the second catalytic cracking catalyst is mixed, the total weight of the second catalytic cracking catalyst and the hydrogen adsorption product and The ratio of the total weight of the vacuum wax oil C is 6.0, and the catalytic cracking reaction occurs together under the conditions of a reaction time of 2.5 seconds, and the apparent average linear velocity of oil and gas in the riser cracking zone II is 22 m/s (fast bed fluidized state) The generated oil and gas enter the fractionation device for fractionation to obtain diesel oil and oil slurry. The rich gas at the top of the fractionation device is not compressed by the rich gas compressor and directly enters the absorption and stabilization device for further product separation to obtain products such as dry gas, liquefied gas and gasoline. Refining ratio 0.1. After reacting for a certain period of time, after the raw catalytic cracking catalyst is stripped to remove the oil gas adsorbed inside it, it is sent to the regenerator using air as the regeneration gas, and it is regenerated by contacting the raw catalytic cracking catalyst at a regeneration temperature of 600-680°C; regeneration The final regenerant is recycled. The operating conditions and product distribution are listed in Table 4.

As can be seen from Table 4, in Example 2, residual oil B and vacuum wax oil C are partitioned to feed catalytic cracking, the residual oil adsorption desulfurization rate is 72% by weight, the nitrogen removal rate is 70% by weight, and the metal removal rate is 45.0% by weight. %; its oil slurry yield is 5.0% by weight, dry gas yield is 2.3% by weight, coke yield is 8.5%, and liquid product yield (liquefied gas yield+gasoline yield+diesel yield) is as high as 84.2% by weight , wherein the yield of gasoline is as high as 39.5% by weight, and the yield of propylene is as high as 5.3% by weight; the sulfur content of the product gasoline is 98.6ppm, and the nitrogen content is 10.1ppm.

Comparative example 2

Carry out catalytic cracking by the same method as Example 2, the difference is that in Comparative Example 2: the hydrogen-containing gas is replaced by hydrogen-free water vapor, the reactor pressure is 0.22MPa, and no cooling medium is injected, and the residual oil B is mixed with The mixture of wax oil C and water vapor is directly injected into the riser cracking zone of the fluidized bed riser reactor, that is, the residue B is directly subjected to catalytic cracking reaction on the second catalytic cracking catalyst without adsorption; after the reaction, the top of the fractionation unit is rich in The gas is compressed and raised to 1.2-1.6MPa by the gas-rich compressor, and then enters the absorption and stabilization device for further product separation; the heavy oil refining ratio is 0.2. The operating conditions and product distribution are listed in Table 4.

As can be seen from Table 4, in comparative example 2, residual oil B is directly mixed with vacuum wax oil C to carry out catalytic cracking reaction without adsorption, and its oil slurry yield is 6.5% by weight, and dry gas yield is 3.4% by weight %, the coke yield is 9.3%, and the liquid product yield (liquefied gas yield+gasoline yield+diesel yield) is 80.8, wherein the gasoline yield is 36.1% by weight, and the propylene yield is 5.0% by weight; the product gasoline sulfur The content is 352.0ppm, and the nitrogen content is 33.6ppm.

As can be seen from the data in Table 4, adopting the method of the present invention to process page residue B and wax oil C has high conversion capacity, low heavy oil re-refining ratio, and low 1.5 percentage points of oil slurry yield, while dry gas and wax oil C The coke yield is low, the dry gas + coke yield is 1.9 percentage points lower, and the liquid product yield is increased by 3.4 percentage points; the sulfur content of the product gasoline is reduced by 253.4ppm, and the nitrogen content is reduced by 23.5ppm.

Example 3

This embodiment is tested according to the flow process of Fig. 3, residual oil B is used as the raw material of catalytic cracking, and test is carried out on the small-sized continuously regenerated descending fluidized bed riser reactor, and residual oil B is fed, and the top of the reactor expands into a streamline. The fluidized bed hydrogen adsorption zone, the diameter of the fluidized bed hydrogen adsorption zone I is 4.2 times the diameter of the riser cracking zone II, the length of the fluidized bed hydrogen adsorption zone I is the length of the riser cracking zone II 30% and a built-in internal heat extraction coil to cool the first catalytic cracking catalyst, and the riser section is transported into the high-temperature second catalytic cracking catalyst; CAT-3 catalyst is used, and the balancer MAT=63. After being preheated at 350°C, the residual oil enters the top of the enlarged fluidized bed adsorption reaction zone I of the reactor. With the hydrogen-containing gas flowing from top to bottom, under the reaction pressure of 1.8MPa, with the addition of 70% of the The mixed gas of hydrogen tail gas and part of the dry gas flows from top to bottom as a hydrogen-containing gas. The volume ratio of H ₂ /raw oil is 300. At the adsorption temperature of 420°C, the weight ratio of the first catalytic cracking catalyst to the residual oil is 4.9, the adsorption Under the condition of 8 seconds, the adsorption reaction is carried out to remove impurities such as basic nitrogen compounds, sulfides and heavy metals; the residual oil then descends into the cracking zone II of the descending riser. Ratio 15, under the condition of 1.5 seconds of reaction time, the catalytic cracking reaction occurs together; the generated oil gas enters the fractionation unit to obtain diesel oil and oil slurry, and the rich gas at the top of the fractionation unit is not compressed by the rich gas compressor and directly enters the absorption stabilization unit for further product separation. Dry gas, liquefied gas, gasoline, etc. are obtained, and part of the dry gas is recycled back to the hydrogen adsorption zone I of the fluidized bed as hydrogen-containing gas as required. After reacting for a certain period of time, after the raw catalytic cracking catalyst is stripped to remove the oil gas adsorbed inside it, air is used as the regeneration gas, and it is regenerated by contacting with the raw catalytic cracking catalyst at a regeneration temperature of 600-700°C; The cracking agent is recycled. Operating conditions and product distribution are listed in Table 5.

As can be seen from Table 5, the residual oil B is first subjected to hydrogen adsorption and then catalytic cracking, the adsorption desulfurization rate is 76% by weight, the denitrogenation rate is 85% by weight, and the demetallization rate is 58.0% by weight; the residual oil B is adsorbed and then catalytically cracked , the conversion rate is 67.4% by weight, the yield of oil slurry is 6.0% by weight, the yield of dry gas is 3.3% by weight, the yield of coke is 10.2% by weight, the yield of liquid products is as high as 80.5% by weight, of which the yield of gasoline is as high as 39.4% by weight, and the yield of propylene The rate is as high as 4.4% by weight; the sulfur content of the product gasoline is 96.4ppm, and the nitrogen content is 13.3ppm.

Comparative example 3

This comparative example is with residual oil B as raw material, with CAT-3 as catalyzer, balance agent MAT is 63, tests on the small-scale descending fluidized bed riser catalytic cracking unit of embodiment 3, and what is different from embodiment 3 is: The hydrogen-containing gas is replaced by hydrogen-free water vapor, the reactor pressure is 0.14MPa, and no cooling medium is injected, and the residue B and water vapor are directly injected into the cracking zone of the riser of the fluidized bed reactor, that is, the residue B Downstream with the catalyst, the residual oil directly undergoes catalytic cracking reaction without being adsorbed in a non-hydrogen atmosphere; after the reaction, the rich gas at the top of the fractionation unit is compressed and raised to 1.2-1.6 MPa by the rich gas compressor and then enters the absorption stable The device further separates products; the heavy oil refining ratio is 0.2. Operating conditions and product distribution are listed in Table 5.

As can be seen from Table 5, the residual oil B directly undergoes catalytic cracking reaction without being adsorbed in a non-hydrogen atmosphere, and its conversion rate is 66.9% by weight, the oil slurry yield is 7.5% by weight, the dry gas yield is 4.0% by weight, and the coke production rate is 66.9% by weight. The yield is 11.0% by weight, the yield of liquid product is 77.5% by weight, wherein the yield of gasoline is 38.1% by weight, and the yield of propylene is 4.1% by weight; the sulfur content of product gasoline is 401.5ppm, and the nitrogen content is 88.8ppm.

As can be seen from the data in Table 5, adopting the method of the present invention to process residual oil B, the residual oil conversion capacity is high, the refining ratio is low, the conversion rate increases by 0.5 percentage points, and the oil slurry yield is low by 1.5 percentage points, while The yield of dry gas and coke is low, the yield of dry gas + coke is 1.5 percentage points lower, and the yield of liquid products is increased by 3.0 percentage points; the sulfur content of product gasoline is reduced by 305.1ppm, and the nitrogen content is reduced by 75.5ppm.

Table 1 The properties of the inferior raw material oil used in the embodiments of the present invention and comparative examples

Inferior raw material oil name Shale oil residual oil Decompression wax oil serial number A B C Density (20℃), kg/ ^m3 928 942.7 919 Kinematic viscosity at 100°C, ^mm2 /s 9.03 62.8 8.6 Carbon residue, wt% 3.1 6.5 0.12 freezing point, ℃ twenty four 33 / Asphaltenes, weight % 1.3 2.4 / Colloid, weight % 35.7 13.0 / Elemental composition Carbon, weight % 83.28 86.82 86.33 Hydrogen, weight % 11.65 12.07 12.66 Sulfur, wt% 0.53 0.53 0.64 Nitrogen, wt% 2.34 0.37 0.12 Oxygen, wt% 2.2 0.21 / Metal content, ppm iron 11.0 11.2 1.8 nickel 6.6 7.6 3.8 calcium 0.1 8.5 3.3 vanadium <0.1 8.2 0.4 sodium 1.3 1.2 2.0 Distillation range, ℃ initial boiling point 305 340 347 30% 410 421 420 50% 510 558 437

Table 2 Catalyst CAT-3 used in the embodiments of the present invention and comparative examples

Catalyst number CAT-3 Zeolite type Medium and large pore zeolites Chemical composition, wt% Silicon oxide 52.7 Aluminum oxide 42.0 sodium oxide 0.30 cobalt oxide 1.6 rare earth 3.4 Apparent density, kg/m ³ 750 Pore volume, ml/g 0.40 Specific surface area, ^m2 /g 196 Wear index, weight % ^-1 1.5 Sieve composition, wt% 0～40 microns 20.5 40～80 microns 55.2 >80 microns 24.3

Table 3 is the operating conditions and product distribution of embodiment 1 of the present invention and comparative example 1

Example 1 Comparative example 1 Raw oil Shale Oil A Shale Oil A Feeding method Feed to the hydrogen adsorption zone of the fluidized bed Riser cracking zone feed Catalyst name CAT-3 CAT-3 Balancer Activity (MAT) 65 65 Refinery ratio 0.1 0.3 Reactor top pressure, MPa 4.2 0.22 Operating conditions of the hydrogen adsorption zone of the fluidized bed Raw material preheating temperature, ℃ 260 260 H ₂ /Volume ratio of raw oil 500 / Adsorption temperature, ℃ 300 / Adsorption time, s 12.0 / Catalyst/shale oil weight ratio 4.8 / Desulfurization rate, wt% 82.0 Nitrogen removal rate, wt% 87.0 / Demetallization rate, weight % 62.0 Riser cracking zone operating conditions The temperature of the lower part of the reaction zone, ℃ 530 530 Temperature in the middle of the reaction zone, °C 510 510 Temperature of the upper part of the reaction zone, ℃ 500 500 Catalyst/shale oil weight ratio 6.4 6.4 Oil and gas residence time, s 3.5 3.5 Water vapor/total raw material weight ratio 0.5 0.5 Product distribution, weight % dry gas 2.3 3.0 liquefied gas 16.2 14.5 Propylene 4.9 4.4 gasoline 41.8 39.3 diesel fuel 26.4 26.9 oil slurry 5.5 6.5 Coke 7.8 9.8 total 100.0 100.0 Conversion rate, weight % 68.1 66.6 Liquid product yield, weight % 84.4 80.7 gasoline quality Sulfur content, ppm 52.5 291.5 Nitrogen content, ppm 85.2 458.6

Table 4 is the operating conditions and product distribution of embodiment 2 of the present invention and comparative example 2

Example 2 Comparative example 2 Raw oil 30%B+70%C 30%B+70%C Feeding method Partition feeding mixed feed Catalyst name CAT-3 CAT-3 Balancer Activity (MAT) 65 65 Refinery ratio 0.1 0.2 Reactor top pressure, MPa 3.5 0.22 Operating conditions of the hydrogen adsorption zone of the fluidized bed Raw material preheating temperature, ℃ 300 210 Volume ratio of H ₂ /residue B 500 / Adsorption temperature, ℃ 350 / Adsorption time, s 5.0 / Catalyst/Residue B Weight Ratio 3.0 / Desulfurization rate of residual oil, wt% 72.0 / Nitrogen removal rate of residual oil, wt% 70.0 / Demetallization rate of residual oil, weight % 45.0 / Riser cracking zone operating conditions The temperature of the lower part of the reaction zone, ℃ 540 540 Temperature in the middle of the reaction zone, °C 515 515 The temperature of the upper part of the reaction zone, ℃ 510 510 Catalyst/feed oil (B+C) weight ratio 6.0 6.0 Oil and gas residence time, s 2.5 2.5 Water vapor/total raw material weight ratio 0.5 0.5 Product distribution, weight % dry gas 2.3 3.4 liquefied gas 17.2 16.5 Propylene 5.3 5.0 gasoline 39.5 36.1 diesel fuel 27.5 28.2 oil slurry 5.0 6.5 Coke 8.5 9.3 total 100.0 100.0 Conversion rate, weight % 67.5 65.3 Liquid product yield, weight % 84.2 80.8 gasoline quality Sulfur content, ppm 98.6 352.0 Nitrogen content, ppm 10.1 33.6

Table 5 is the operating conditions and product distribution of the embodiment of the present invention 3 and comparative example 3

Claims (16)

1. a kind of processing method of inferior feedstock oil, this method includes：

A, the fluid bed that hydrogen-containing gas and inferior feedstock oil are sent into fluid bed riser reactor face hydrogen and inhaled Contacted in attached area (I) with the first catalytic cracking catalyst and carry out facing hydrogen adsorption reaction, obtain facing hydrogen suction Accessory substance；

B, gained in step a faced into the lifting that hydrogen adsorbed product sends into the fluid bed riser reactor Contacted in the pipe zone of cracking (II) with the second catalytic cracking catalyst and carry out catalytic cracking reaction, urged Change cracking oil gas.

2. processing method according to claim 1, this method also includes：By gained in step b Cycle oil pneumatic transmission enters fractionating device (8) and carries out fractionation processing, obtains including the catalytic cracking of rich gas Product；Gained rich gas is sent directly into absorption stabilizing apparatus (10) without rich gas compressor to be absorbed Stable processing.

3. processing method according to claim 1, this method also includes：In stepb, will Conventional catalytic cracking feedstock oil with it is described face hydrogen adsorbed product together with carry out the catalytic cracking reaction；Its In, the Conventional catalytic cracking feedstock oil is at least one in wax oil, reduced crude and decompressed wax oil Kind.

4. processing method according to claim 1, wherein, the hydrogen-containing gas include hydrogen and/ Or dry gas, the inferior feedstock oil is selected from shale oil, liquefied coal coil, tar sand oil, wax tailings, slag At least one of oil, hydrogenated residue and deasphalted oil.

5. processing method according to claim 1, wherein, first catalytic cracking catalyst It is identical with the composition of the second catalytic cracking catalyst, zeolite, 5-99 weight % including 1-50 weight % Inorganic oxide and 0-70 weight % clay.

6. processing method according to claim 5, wherein, the zeolite include mesopore zeolite and/ Or large pore zeolite, the mesopore zeolite is selected from ZSM-5 zeolite, ZSM-11 zeolites, ZSM-12 boilings Stone, ZSM-23 zeolites, ZSM-35 zeolites, ZSM-38 zeolites, ZSM-48 zeolites and ZRP zeolites At least one of, the large pore zeolite is selected from rare earth Y type zeolite, rare earth hydrogen Y zeolites, high silicon Y At least one of type zeolite and ultrastable；The inorganic oxide is silica and/or oxidation Aluminium；The clay be selected from silica, kaolin, halloysite, montmorillonite, diatomite, angstrom At least one of Lip river stone, saponite, rectorite, sepiolite, attapulgite, hydrotalcite and bentonite.

7. processing method according to claim 1, wherein, first catalytic cracking catalyst For the fresh catalyst Cracking catalyst of supplement, the regeneration catalyzing Cracking catalyst of cooling, the semi regeneration cooled down At least one of catalytic cracking catalyst and the catalytic cracking catalyst to be generated of cooling, second catalysis Cracking catalyst is regeneration catalyzing Cracking catalyst；The temperature of first catalytic cracking catalyst is 200-500 DEG C, the temperature of the second catalytic cracking catalyst is 580-680 DEG C.

8. processing method according to claim 1, wherein, the condition for facing hydrogen adsorption reaction Including：Temperature is 200-450 DEG C, and pressure is 0.5-5.0 MPas, and adsorption time is 1-90 seconds, agent oil weight Amount is than being (0.5-5)：1, hydrogen to oil volume ratio is 100-1000；The condition of the catalytic cracking reaction includes： Temperature is 460-540 DEG C, and pressure is 0.5-5.0 MPas, and the oil gas residence time is -15 seconds 0.5 second, agent oil Weight ratio is (5-30)：1.

9. processing method according to claim 1, this method also includes：Cooling medium is sent into The fluid bed, which faces, carries out temperature control in hydrogen adsorption zone (I)；The cooling medium be selected from cold hydrogen, water, At least one of gasoline, diesel oil, recycle oil and fused salt.

10. a kind of system of processing of inferior feedstock oil, it is characterised in that the system of processing includes being provided with Fluid bed is formed with the fluid bed riser reactor of fluid bed section and lifting pipeline section, the fluid bed section Face in hydrogen adsorption zone (I), the lifting pipeline section and be formed with riser cracking area (II)；

The fluid bed faces hydrogen adsorption zone (I) and connects and be in fluid communication with riser cracking area (II), The fluid bed section is provided with hydrogen-containing gas entrance, inferior raw material oil-in and the first catalytic cracking catalyst Entrance, the lifting pipeline section be provided with the second catalytic cracking catalyst entrance, catalytic cracking oil gas outlet and Catalytic cracking catalyst is exported, and sets or be not provided with Conventional catalytic cracking raw material oil-in.

11. system of processing according to claim 10, wherein, the system of processing also includes dividing Distillation unit (8) and absorption stabilizing apparatus (10), the oil gas entrance of the fractionating device (8) with it is described Catalytic cracking oil gas communication, the rich gas outlet of the fractionating device (8) absorbs steady with described The rich gas entrance for determining device (10) is in fluid communication.

12. system of processing according to claim 10, wherein, the system of processing also includes again Raw device (13), the regenerator (13) is provided with regenerator catalyst outlet and regenerator catalyst enters Mouthful, the regenerator catalyst outlet is split with the first catalytic cracking catalyst entrance and the second catalysis Change catalyst inlet connection, the regenerator catalyst entrance is exported with the catalytic cracking catalyst to be connected It is logical.

13. system of processing according to claim 12, wherein, the regenerator catalyst outlet Connected by heat collector (17) with the first catalytic cracking catalyst entrance.

14. system of processing according to claim 10, wherein, the lifting pipeline section is upstriker Riser reactor, the fluid bed section is located at the lower section of lifting pipeline section, and first catalytic cracking is urged Agent entrance is located at the bottom of the fluid bed section, and the second catalytic cracking catalyst entrance is located at described The bottom of pipeline section is lifted, the catalytic cracking catalyst outlet is located at the top of the lifting pipeline section；

Or, the lifting pipeline section is downstriker riser reactor, and the fluid bed section is located at riser The top of section, and the first catalytic cracking catalyst entrance is located at the top of the fluid bed section, it is described Second catalytic cracking catalyst entrance is located at the top of the lifting pipeline section, and the catalytic cracking catalyst goes out Mouth is located at the bottom of the lifting pipeline section.

15. system of processing according to claim 10, wherein, the fluid bed faces hydrogen adsorption zone (I) 0.5-5 times of the diameter of a diameter of riser cracking area (II), the fluid bed faces hydrogen absorption The length in area (I) is the 1-30% of the length of riser cracking area (II).

16. system of processing according to claim 10, wherein, the fluid bed section is provided with cold But medium inlet, the cooling medium entrance faces hydrogen adsorption zone (I) directly fluid with the fluid bed and connected Heat collector (17) that is logical or facing with being arranged on the fluid bed in hydrogen adsorption zone (I) is in fluid communication.