TWI399431B - A method for producing light fuel oil from inferior raw material oils - Google Patents

Description

Method for preparing light fuel oil from inferior raw material oil

The present invention relates to a catalytic conversion process for hydrocarbon oils, and more particularly to a process for converting inferior feedstock oil into a large amount of light fuel oil.

The quality of crude oil is getting worse with the increase of crude oil production, mainly due to the increase of crude oil density, high viscosity, heavy metal content, sulfur content, nitrogen content, colloid and asphaltene content and acid value. At present, the price difference between inferior crude oil and high-quality crude oil is increasing with the shortage of petroleum resources, which leads to the increasing attention of low-quality inferior crude oil mining and processing methods, that is, from the poor quality crude oil as much as possible. The yield of light oil, which brings great challenges to the processing technology of traditional crude oil.

The traditional heavy oil processing is divided into three types of processing workers, the first is hydrogen chemical workers, mainly including hydrotreating and hydrorefining; the second is decarbonizing workers, mainly including solvent deasphalting, delayed coking and heavy oil catalytic cracking; The three types are aromatics extraction workers. Inferior heavy oil can improve the hydrogen to carbon ratio through these three types of engineering techniques, and convert inferior hydrocarbons into low boiling compounds. When inferior heavy oil is treated by decarburization, the content of sulfur, nitrogen and heavy metals in inferior heavy oil and the content of aromatics, colloid and asphaltenes have great influence on decarbonization workers. The problem of decarbonization workers is the yield of liquid products. Low, the product is poor in nature and needs to be processed. Like delayed coke chemical workers, although the impurity removal rate is high, the coke yield is more than 1.5 times the residual carbon value of the feedstock oil, and how to use the solid coke is also a problem to be solved. Hydrotreating workers can make up for the shortage of decarburization workers. After the inferior heavy oil is hydrotreated, the liquid product yield is high and the product properties are good, but the hydrogenation treatment method often has a large investment. The aromatics extracting tool has the characteristics of small investment and fast return, not only can achieve good results in heavy oil processing, but also an important chemical raw material that is by-product is aromatic hydrocarbon.

In view of the respective advantages and disadvantages of hydrogen chemical workers and decarbonization workers, CN1448483A discloses a combination method of hydrogen chemical workers and decarbonization workers, which is to firstly carry out the thermal cracking of the residue feed, and then with the catalytic cracking. The slurry is subjected to solvent deasphalting together, and the deasphalted oil is subjected to hydrogenation treatment in the presence of a hydrogenation catalyst and hydrogen. The method not only reduces the severity of the residue hydrogenation device, but also prolongs the service life of the hydrogenation catalyst, and improves the yield and properties of the liquid product, but the deoiled asphalt is difficult to utilize.

CN1844325A discloses a method for organic combination of decarbonization workers and hydrogen chemical workers for treating heavy oil, which combines inferior heavy oil through solvent deasphalting workers and coke chemical workers, and treated deasphalted oil and coking wax oil as The raw material of the heavy oil hydrotreating unit improves the feed properties of the heavy oil hydrotreating unit, moderates the operating conditions of the heavy oil hydrotreating unit, extends the operating cycle of the heavy oil hydrotreating unit, and provides high quality feedstock for downstream catalytic cracking and other equipment. However, the method has a complicated work process and a low liquid yield.

CN1382776A discloses a combination of residue hydrotreating treatment and heavy oil catalytic cracking, which is a residue and a slurry eluate, a catalytic cracking re-sulfurized oil, an optional distillate oil, and a hydrogenation catalyst, in a hydrogenation and hydrogenation catalyst. The hydrogenation reaction is carried out in the presence of hydrogenation; after the steam produced by the reaction is distilled off, the hydrogenated residue enters the catalytic cracking unit together with the optional vacuum gas oil, and the cracking reaction is carried out in the presence of the cracking catalyst, and the heavy cycle oil obtained by the reaction enters the slag. In the oil hydrogenation unit, the distillate slurry is returned to the hydrogenation unit. The method can convert oil slurry and heavy cycle oil into light oil products, and improve the yield of gasoline and diesel oil. Although heavy oil can be produced by hydro-treatment workers, catalytic cracking workers can produce more liquid products, and the product has low impurity content and improved properties. However, when heavy oil has high density, high viscosity, heavy metal, colloid and asphaltene content. When the temperature is high, the operating conditions of the hydrotreating unit are very harsh, the operating pressure is high, the reaction temperature is high, the space velocity is low, the starting period is short, the operating cost is high, and the disposal investment of the device is also high. The properties of the catalytic cracking feedstock oil provided by the residue hydrogenation unit from the initial stage to the end of the operation are constantly changing, thereby adversely affecting the operation of the catalytic cracking unit. The composition of the feedstock oil processed by the residue hydrogenation technology is extremely complicated. The feedstock oil contains not only sulfur, nitrogen and metals, but also alkanes, cycloalkanes and aromatics. The alkane molecules are prone to cracking during hydrogenation to form small molecular hydrocarbons. Even dry gas, resulting in heavy oil resources not being used effectively. At the same time, when the hydrogenated residue oil enters the catalytic cracking unit, it still produces 8~10% by weight of heavy oil, which also causes the utilization efficiency of heavy oil resources to decrease. Returning to the residue hydrogenation unit, but the heavy oil and the residue have a large difference in properties, and the hydrogen content is low, even if the hydrogenation treatment, the improvement of the properties of the heavy oil is limited.

CN1746265A discloses a catalytic cracking processing worker for inferior oil, which returns a light diesel oil fraction obtained by catalytic cracking of inferior oil to a catalytic cracking unit for refining, and the obtained heavy oil fraction is subjected to solvent extraction, and the extracted heavy aromatic hydrocarbon is used as a product. The raffinate oil is returned to the catalytic cracking unit for refining. The method solves the problem of heavy oil to some extent, but the method needs to control the end point of the light diesel oil fraction. , the end point of heavy diesel The light diesel oil fraction is returned to the catalytic cracking unit for refining, the heavy diesel oil is extracted into the aromatic hydrocarbon extraction unit, and the raffinate oil is returned to the catalytic cracking unit. As a result, although the amount of oil slurry is reduced, it is still relatively high, and there is no diesel product, and the dry Gas production is also large.

CN1766059A discloses a method for treating inferior heavy oil or residual oil, which firstly inputs heavy oil or residual oil raw material into a solvent extraction device, and the obtained deasphalted oil enters a fixed bed hydrotreating device for hydrogenation treatment, and the obtained hydrogenated tail oil enters the catalytic cracking device. Wherein part or all of the obtained slurry is fed to the suspended bed hydrogenation unit together with the deasphalted oil obtained by solvent extraction, and the product is separated to obtain a light fraction and an unconverted tail oil, wherein the unconverted tail oil is recycled to the solvent extraction apparatus. The method organically combines catalytic cracking workers, extraction workers and hydrogen chemical workers, and has certain effects on heavy oil treatment, but the method has complicated engineering process and low liquid yield.

With the development of oil recovery technology, a large amount of high acid and high calcium crude oil was extracted. The calcium contaminants in crude oil are mainly non-porphyrin organic calcium compounds, which are only soluble in petroleum fractions. The traditional desalination method cannot separate these organic calcium compounds from crude oil. When the acid value in crude oil exceeds 0.5 mg KOH/g, it will Corrosion of equipment, traditional atmospheric and vacuum equipment is difficult to process high acid crude oil. To this end, CN1827744A discloses a method for processing high acid value crude oil by preheating a crude oil having a total acid value of more than 0.5 mgKOH/g after preheating into a fluid catalytic cracking reactor for contact with a catalyst, and The reaction is carried out under the conditions of catalytic cracking reaction, the oil and gas after the reaction are separated, the reaction oil is sent to the subsequent separation system, and the reacted catalyst is recycled after being stripped and regenerated. The method has the advantages of strong industrial practicability, low operation cost and good deacidification effect, but the dry gas and coke yield are high, resulting in a decrease in the utilization efficiency of petroleum resources.

It has long been recognized by those of ordinary skill in the art that the higher the conversion of heavy oil catalytic cracking, the better. However, the inventors have creatively thought and repeated experiments and found that the conversion rate of heavy oil catalytic cracking is not as high as possible. When the conversion rate is high to a certain extent, the target product increases little, and the yield of dry gas and coke is greatly increased.

In order to efficiently utilize inferior heavy oil resources to meet the growing demand for light fuel oils, it is necessary to develop a catalytic conversion process for converting inferior heavy oil feedstock into a large number of light and clean fuel oils.

The technical problem to be solved by the present invention is to catalytically convert a poor quality heavy oil feedstock into a large amount of clean light fuel oil.

The method of the invention comprises the following steps:

(1) The preheated inferior feedstock oil enters the first reaction zone of the catalytic conversion reactor and is contacted with the hot catalytic conversion catalyst to generate a cracking reaction, and the generated oil and gas and used catalyst are optionally combined with light feedstock oil and/or cold. After the mixed medium is mixed, it enters the second reaction zone of the catalytic conversion reactor, and undergoes a cracking reaction, a hydrogen transfer reaction and an isomerization reaction. After the reaction product and the carbon-containing catalyst to be reacted, the reaction product enters the separation system. Separated into dry gas, liquefied gas, gasoline, diesel and catalytic wax oil. Optionally, the catalyst to be produced is steam stripped and sent to a regenerator for charring regeneration, and the hot regenerated catalyst is returned to the reactor for recycling; The first reaction zone and the second reaction zone reaction conditions are characterized in that the reaction obtains a catalytic wax oil product comprising 12% to 60% by weight, preferably 20% to 40% by weight, based on the feedstock oil;

(2) the catalytic wax oil enters a hydrotreating unit or 1 and an aromatic hydrocarbon extraction unit to obtain a hydrogenated catalytic wax oil or/and a raffinate oil;

(3) The hydrogenation catalytic wax oil or/and raffinate oil is recycled to the first reaction zone of the catalytic conversion reactor of step (1) or/and other catalytic converters for further reaction to obtain the desired product light fuel oil.

The technical solution of the present invention is embodied as follows:

The preheated inferior feedstock oil is contacted with the hot regenerated catalytic converter catalyst in the first reaction zone of the catalytic converter reactor under the action of water vapor, and the reaction temperature is 510 ° C ~ 650 ° C, preferably 520 ° C ~ 600 ° C, The weight hourly space velocity is 10~200h ^{-1 is} preferably 15~150h ^-1 , and the weight ratio of catalyst to feedstock oil (hereinafter referred to as the ratio of agent to oil) is 3~15:1, preferably 4~12:1, water vapor and The weight ratio of the feedstock oil (hereinafter referred to as the water-oil ratio) is 0.03 to 0.3:1, preferably 0.05 to 0.2:1, and the pressure is 130 kPa to 450 kPa, and the macromolecular cracking reaction occurs to remove the metal and sulfur in the inferior feedstock oil. At least one impurity of nitrogen, naphthenic acid;

The generated oil and gas and the used catalyst are optionally mixed with the light feedstock oil and/or the cold shock medium and then enter the second reaction zone of the catalytic conversion reactor at a reaction temperature of 420 ° C to 550 ° C, preferably 460 ° C to 530 The cracking reaction, hydrogen transfer reaction and isomerization reaction are carried out under conditions of a temperature hourly space velocity of 5 to 150 h ^{-1 and} preferably 15 to 80 h ^-1 ; the reaction product is separated to obtain dry gas and liquefied gas (including propylene, propane and C ₄ hydrocarbon), gasoline, diesel and catalytic wax oil, wherein propane, C ₄ hydrocarbon, diesel oil can also be used as the light feedstock oil in the second reaction zone;

The catalytic wax oil is separately or mixed with diesel oil and/or other heavy oil, and then enters a hydrotreating reactor, and the hydrogenated oil is stripped to remove light hydrocarbon molecules, and the stripped hydrogenated catalytic wax oil is recycled to the catalytic conversion. The first reaction zone of the reactor or/and other catalytic converters are further reacted to provide the desired product propylene and light fuel oil.

Or / and the catalytic wax oil enters the aromatics extraction device, is treated by an existing aromatics extraction worker, and the oil is extracted as an aromatic hydrocarbon-rich chemical raw material, and the raffinate oil is recycled to the first reaction zone of the catalytic conversion reactor or/and Further catalytic converters are further reacted to obtain the desired product propylene and light fuel oil.

The resulting hydrogenated catalytic wax oil or/and raffinate oil is recycled to the first reaction zone of the catalytic conversion reactor or/and other catalytic converters for further reaction to obtain the desired product propylene and light fuel oil.

Other catalytic converter units are conventional catalytic cracking units and their various improved apparatus. For a more detailed description, see CN1232069A and CN1232070A.

The inferior feedstock oil is heavy petroleum hydrocarbon and/or other mineral oil, wherein the heavy petroleum hydrocarbon is selected from the group consisting of vacuum residue (VR), inferior atmospheric residue (AR), inferior hydrogenated residue, coking gas. Any mixture of one or more of oil, deasphalted oil, high acid crude oil, high metal crude oil; other mineral oils are one or more of coal liquefied oil, oil sand oil, shale oil.

The properties of the inferior feedstock oil satisfy at least one of the following indicators:

The density is 900~1000 kg/ ^m3 , preferably 930~960 kg/ ^m3 ; the residual carbon is 4~15 wt%, preferably 6~12 wt%; the metal content is 15~600 ppm, preferably 15~ 100 ppm; acid value of 0.5 to 20 mg KOH/g, preferably 0.5 to 10.0 mg KOH/g.

The light feedstock oil is selected from one or more of liquefied gas, gasoline, diesel oil, the liquefied gas obtained from the liquefied gas obtained by the method and/or other methods; the gasoline is selected from the method The resulting gasoline and/or other method of obtaining gasoline; the diesel fuel is selected from the diesel fuel obtained by the method and/or other methods.

The catalytic wax oil is a catalytic wax oil produced by the present device or an external device such as conventional catalytic cracking. The catalytic wax oil has a cutting point of not less than 250 ° C, a hydrogen content of not less than 10.5% by weight, a more preferable cutting point of not less than 300 ° C, more preferably not less than 330 ° C, and a hydrogen content of not less than 10.8 % by weight. .

The hydrogenation catalytic wax oil is obtained by subjecting the apparatus or the apparatus to hydrogenation treatment of a catalytic wax oil produced by an external apparatus such as a conventional catalytic cracking. Hydrogenated catalytic wax oil is used as a feedstock oil for conventional catalytic cracking units.

The raffinate oil is obtained by extracting the catalytic wax oil produced by the present device or the external device, such as conventional catalytic cracking, by aromatic hydrocarbon extraction. The raffinate oil is used as a feedstock oil for a conventional catalytic cracking unit.

The cold shock medium is a mixture of any one or more selected from the group consisting of a cold shock agent, a cooled regenerated catalyst, a cooled semi-regenerated catalyst, a spent catalyst, and a fresh catalyst, wherein the cold shock agent is selected from the group consisting of liquefaction. a mixture of one or more of gas, crude gasoline, stabilized gasoline, diesel, heavy diesel or water; the cooled regenerated catalyst and the cooled semi-regenerated catalyst are cooled by two stages of regeneration of the catalyst to be produced and after a period of regeneration The carbon content of the regenerated catalyst is 0.1% by weight or less, preferably 0.05% by weight or less, and the carbon content of the semi-regenerated catalyst is 0.1% by weight to 0.9% by weight, preferably the carbon content is 0.15% by weight to 0.7% by weight; The catalyst carbon content is 0.9% by weight or more, and preferably the carbon content is 0.9% by weight to 1.2% by weight.

The gasoline or diesel distillation range is adjusted as needed, including but not limited to full range gasoline or diesel. The catalytic conversion catalyst comprises a zeolite, an inorganic oxide and an optional clay, and the components respectively comprise the total weight of the catalyst: 1% by weight to 50% by weight of the zeolite, 5% by weight of the inorganic oxide, and 99% by weight of the clay. %-70% by weight. Wherein zeolite is used as the active component, selected from medium pore zeolites and/or optionally large pore zeolites, and the medium pore zeolite comprises from 0% by weight to 100% by weight, preferably from 0% by weight to 50% by weight, based on the total weight of the zeolite, more preferably 0. The heavy pore zeolite accounts for 0% by weight to 100% by weight, preferably 20% by weight to 80% by weight, based on the total weight of the zeolite. The medium pore zeolite is selected from the ZSM series zeolite and/or the ZRP zeolite, and the above-mentioned medium pore zeolite may be modified with a non-metal element such as phosphorus and/or a transition metal element such as iron, cobalt or nickel, and a more detailed description of the ZRP. See US 5,232,675, one or more of the ZSM series zeolites selected from the group consisting of ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48, and other similarly structured zeolites. For a more detailed description of ZSM-5, see US 3,702,886. The macroporous zeolite is selected from a mixture of one or more of the group consisting of rare earth Y (REY), rare earth hydrogen Y (REHY), super stable Y obtained by various methods, and high yttrium Y.

The inorganic oxide is used as a binder and is selected from the group consisting of cerium oxide (SiO ₂ ) and/or aluminum oxide (Al ₂ O ₃ ).

The clay acts as a substrate (i.e., a carrier) selected from the group consisting of kaolin and/or halloysite.

The catalyst may also be a spent equilibrium catalyst used in conventional catalytic cracking units.

The catalytic cracking of the two reaction zones in the process can be applied to the same type of catalyst, and can also be applied to different types of catalysts. Different types of catalysts can be catalysts with different particle sizes and/or catalysts with different apparent bulk densities. Different types of zeolites may also be used for the active components of the catalysts having different particle sizes and/or different apparent bulk densities. Catalysts of different sizes and/or catalysts of high and low apparent bulk density may enter different reaction zones, for example, a catalyst containing large particles of ultra-stable Y-type zeolite enters the first reaction zone, increasing the cracking reaction, containing rare earth Y-type The small particle catalyst of zeolite enters the second reaction zone, and the hydrogenation transfer reaction is carried out. The catalysts with different particle sizes are stripped in the same stripper and regenerated in the same regenerator, and then the large particles and small particle catalysts are separated, and the small particle catalyst is cooled. Enter the second reaction zone. Catalysts with different particle sizes are demarcated between 30 and 40 microns, and catalysts with different apparent bulk densities are demarcated between 0.6 and 0.7 g/cm ³ .

The reactor suitable for the catalytic cracking unit may be one selected from the group consisting of a constant diameter riser, a constant line riser, a variable diameter riser or a fluidized bed, or may be composed of an equal diameter riser and a fluidized bed. Composite reactor. It is preferred to use a variable diameter riser reactor or a composite reactor of equal diameter riser and fluidized bed.

The fluidized bed reactor is selected from the group consisting of a riser, a constant velocity fluidized bed, a fluidized bed of equal diameter, an upstream conveyor line, and one or more series or parallel combinations of downstream conveyor lines. . The riser can be a conventional equal-diameter riser or a riser of various forms. The gas velocity of the fluidized bed is 0.1 m/sec to 2 m/sec, and the gas velocity of the riser is 2 m/sec to 30 m/sec (excluding the catalyst).

The preferred embodiment of the invention is carried out in a variable diameter riser reactor, see CN 1237477 A for a more detailed description of the reactor.

The hydrogenation treatment unit is in contact with a hydrogenation treatment catalyst in the presence of hydrogen, and has a hydrogen partial pressure of 3.0 to 20.0 MPa, a reaction temperature of 300 to 450 ° C, a hydrogen oil volume ratio of 300 to 2000 v/v, and a volumetric space velocity of 0.1 to 3.0. Hydrogenation is carried out under the reaction conditions of h ^-1 .

The method aromatics extraction unit is suitable for use in existing aromatics extraction units. The solvent for extracting the aromatic hydrocarbon is selected from one or more of furfural, dimethyl hydrazine, dimethylformamide, monoethanolamine, ethylene glycol, and 1,2-propanediol, and the solvent can be recovered, and the extraction temperature is The ratio of the solvent to the catalytic wax oil is from 0.5 to 5.0:1 at 40 to 120 °C.

The technical scheme combines catalytic cracking, hydrogenation treatment, aromatic hydrocarbon extraction and traditional catalytic cracking to produce propylene and light fuel oil, especially high-octane gasoline, from inferior feedstock oil, thereby achieving efficient oil resources. use. Compared with the prior art, the invention has the following technical effects:

1. The inferior catalytic wax oil is first subjected to catalytic cracking, followed by hydrogenation or/and aromatic extraction, whereby the raw material properties of the hydrotreating or/and aromatics extraction device are significantly improved;

2. The properties of the feedstock oil processed by the hydrotreatment or/and the aromatics extraction unit are improved, so that the operation cycle of the hydrotreatment unit or/and the aromatics extraction unit is significantly improved;

3. After catalytic cracking of inferior heavy oil, the obtained catalytic wax oil contains more polycycloalkanes and less long-chain alkanes, so that the properties of hydrogenation-catalyzed wax oil can be more obviously improved, and the light generated by hydrogenation treatment is light. Hydrocarbon molecules, especially dry gas, are also significantly reduced; the obtained catalytic wax oil is extracted, and the extracted oil is rich in bicyclic aromatic hydrocarbons, which is a good chemical raw material. The raffinate oil is rich in alkanes and naphthenes and is very suitable for catalytic conversion.

4. The hydrocracking unit or/and the extracting unit provide stable catalytic cracking feedstock oil from the initial stage to the end of the operation, thereby facilitating the operation of the catalytic cracking unit;

5. The properties of the hydrogenated catalytic wax oil and/or the catalytic wax oil raffinate oil are improved, so that the light oil yield is obviously increased, the oil slurry yield is obviously reduced, and the petroleum resource is utilized efficiently.

The method provided by the present invention will be further described below with reference to the accompanying drawings, but does not limit the invention.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing the construction process of a first embodiment of the present invention, in which a hydrogenation catalytic wax oil is circulated to a first reaction zone of the catalytic conversion reactor of the present process.

The engineering process is as follows:

The pre-lifting medium enters through the lower part of the riser reactor 2 via the pipeline 1, and the regenerated catalytic conversion catalyst from the pipeline 16 moves upward along the riser under the lifting action of the pre-lifting medium, and the inferior raw material oil passes through the pipeline 3 and the mist from the pipeline 4. The steam is injected into the lower portion of the reaction zone I of the riser 2, mixed with the existing stream of the riser reactor, and the inferior feedstock undergoes a cracking reaction on the hot catalyst and moves upward. The light feedstock oil is injected into the lower portion of the reaction zone II of the riser 2 via line 5 and the atomized steam from line 6, and is mixed with the existing stream of the riser reactor. The light feedstock oil is on the catalyst with a lower amount of carbon deposits. The cracking reaction occurs and moves upwards, and the generated oil and gas and the deactivated catalyst to be produced enter the cyclone separator in the settler 8 through the pipeline 7, thereby realizing the separation of the catalyst to be produced and the oil and gas, and the oil and gas enters the gas collection chamber 9, the catalyst fine powder Return to the settler from the material leg. The catalyst to be produced in the settler flows to the stripping section 10 in contact with the steam from line 11. The oil gas stripped from the catalyst to be produced enters the gas collection chamber 9 through the cyclone separator. The stripped catalyst after the stripping enters the regenerator 13 through the inclined tube 12, and the main wind enters the regenerator through the pipeline 14, burns off the coke on the catalyst to be produced, regenerates the deactivated catalyst, and the flue gas enters the smoke through the pipeline 15. machine. The regenerated catalyst enters the riser via the inclined tube 16.

The oil in the plenum 9 passes through the large oil and gas pipeline 17 and enters the subsequent separation system 18, and the separated propylene is taken out through the line 20, the separated propane is taken out through the line 21, and the C ₄ hydrocarbon is taken out through the line 22, propane and C. ₄ hydrocarbons can be recycled as part of the light feedstock oil to the riser 2 reaction zone II of the catalytic converter unit via lines 30 and 29, respectively. The catalytic cracked dry gas is taken up via line 19, the gasoline fraction is withdrawn via line 23, and the diesel fraction is passed through the tube. Line 24 is taken out, and the diesel fraction can be recycled as part of the light feedstock oil to the riser 2 reaction zone II of the catalytic converter unit via line 28, and the catalytic wax oil fraction is sent to the hydrotreating unit 32 via line 25, and the light is separated. The components are withdrawn via line 26 and the hydrogenated catalytic wax oil is recycled via line 27 to the riser 2 reaction zone I of the catalytic converter unit to further produce low olefin high octane gasoline, propylene and diesel.

2 is a schematic view of a hydraulic process of a second embodiment of the present invention, in which hydrogenated catalytic wax oil is recycled to other catalytic converters. The engineering process of this embodiment is substantially the same as that of the first embodiment, the only difference being that the hydrogenated catalytic wax oil enters another set of catalytic converters 31 via line 27 to further produce low olefin high octane gasoline, propylene, and diesel. (not shown in the figure).

3 is a schematic view of a hydraulic process of a third embodiment of the present invention, in which the raffinate oil is recycled to the first reaction zone of the catalytic conversion reactor of the present process.

The engineering process is as follows:

The pre-lifting medium enters through the lower part of the riser reactor 2 via the pipeline 1, and the regenerated catalytic conversion catalyst from the pipeline 16 moves upward along the riser under the lifting action of the pre-lifting medium, and the inferior raw material oil passes through the pipeline 3 and the mist from the pipeline 4. The steam is injected into the lower portion of the reaction zone I of the riser 2, mixed with the existing stream of the riser reactor, and the inferior feedstock undergoes a cracking reaction on the hot catalyst and moves upward. The light feedstock oil is injected into the lower portion of the reaction zone II of the riser 2 via line 5 and the atomized steam from line 6, and is mixed with the existing stream of the riser reactor. The light feedstock oil is on the catalyst with a lower amount of carbon deposits. The cracking reaction occurs and moves upwards, and the generated oil and gas and the deactivated catalyst to be produced enter the cyclone separator in the settler 8 through the pipeline 7, thereby realizing the separation of the catalyst to be produced and the oil and gas, and the oil and gas enters the gas collection chamber 9, the catalyst fine powder Return to the settler from the material leg. The catalyst to be produced in the settler flows to the stripping section 10 in contact with the steam from line 11. The oil gas stripped from the catalyst to be produced enters the gas collection chamber 9 through the cyclone separator. The stripped catalyst after the stripping enters the regenerator 13 through the inclined tube 12, and the main wind enters the regenerator through the pipeline 14, burns off the coke on the catalyst to be produced, regenerates the deactivated catalyst, and the flue gas enters the smoke through the pipeline 15. machine. The regenerated catalyst enters the riser via the inclined tube 16.

The oil in the plenum 9 passes through the large oil and gas pipeline 17 and enters the subsequent separation system 18, and the separated propylene is taken out through the line 20, the separated propane is taken out through the line 21, and the C ₄ hydrocarbon is taken out through the line 22, propane and C. ₄ hydrocarbons can be recycled as part of the light feedstock oil to the riser 2 reaction zone II of the catalytic converter unit via lines 30 and 29, respectively. The catalytic cracked dry gas is taken up via line 19, the gasoline fraction is withdrawn via line 23, and the diesel fraction is passed through the tube. Line 24 is taken out, and the diesel fraction can be recycled as part of the light feedstock oil to the riser 2 reaction zone II of the catalytic converter unit via line 28, and the catalytic wax oil is sent to the aromatics extraction unit 32 via line 25, and the extracted oil is withdrawn via line 26. The raffinate oil is recycled via line 27 to the reaction zone I of the riser 2 of the above catalytic converter to further produce low olefin high octane gasoline, propylene and diesel.

4 is a schematic view showing the flow of a working process according to a fourth embodiment of the present invention, in which the raffinate oil is circulated to other catalytic converters. The engineering process of this embodiment is substantially the same as that of the third embodiment, the only difference being that the raffinate oil enters another set of catalytic converters 31 via line 27 to further produce low olefin high octane gasoline, propylene, and diesel ( Not shown in the figure).

The following examples will further illustrate the method, but do not limit the method accordingly.

The raw materials used in the examples were vacuum residue, inferior atmospheric residue, inferior hydrogenated residue and acid-containing crude oil, and their properties are shown in Table 1.

The preparation method of the catalytic cracking catalyst GZ-1 used in the examples is briefly described as follows:

1), 20g of NH ₄ Cl is dissolved in 1000g of water, and 100g (dry basis) crystallized product ZRP-1 zeolite is added to the solution (produced by Qilu Petrochemical Company catalyst plant, SiO ₂ /Al ₂ O ₃ =30, rare earth content) RE ₂ O ₃ = 2.0% by weight), after exchanged at 90 ° C for 0.5 h, the filter cake was filtered; 4.0 g of H ₃ PO ₄ (concentration 85%) and 4.5 g of Fe(NO ₃ ) _{3 were} dissolved in 90 g of water, The filter cake is mixed and dipped and dried; then calcined at 550 ° C for 2 hours to obtain a MFI structure mesoporous zeolite containing phosphorus and iron, and the elemental analytical chemical composition thereof is

0.1Na ₂ O‧5.1Al ₂ O ₃ ‧2.4P ₂ O ₅ ‧1.5Fe ₂ O ₃ ‧3.8RE ₂ O ₃ ‧88.1SiO ₂ .

2), using 7500kg of polyhydrate kaolin (Suzhou Ceramics Industrial Products, solid content 71.6wt%) with 250kg of deionized water, and then adding 54.8kg of pseudo-boehmite (industrial products of Shandong Aluminum Factory, solid content 63wt%) Adjust the pH to 2-4 with hydrochloric acid, stir evenly, let stand for 1 hour at 60-70 ° C, keep the pH at 2-4, lower the temperature to below 60 ° C, add 41.5Kg aluminum sol (Qilu Petrochemical) The company's catalyst plant product, Al ₂ O ₃ content of 21.7 wt%), was stirred for 40 minutes to obtain a mixed slurry.

3), the phosphorus- and iron-containing MFI structure of the pore-prepared zeolite (dry basis is 2 kg) and DASY zeolite (Qilu Petrochemical Company catalyst factory industrial product prepared by the step 1), the unit cell size is 2.445-2.448 nm, and the dry basis is 22.5kg) is added to the mixed slurry obtained in the step 2), stirred uniformly, spray-dried, washed with ammonium dihydrogen phosphate solution (phosphorus content of 1 wt%), washed away with free Na ⁺ , and dried to obtain a catalytic cracking catalyst sample. The composition of the catalyst was 2% by weight of MFI structure mesoporous zeolite containing phosphorus and iron, 18% by weight of DASY zeolite, 32% by weight of pseudoboehmite, 7% by weight of aluminum sol and the balance of kaolin.

The preparation method of the hydrotreating catalyst used in the examples is as follows: ammonium metatungstate ((NH ₄ ) ₂ W ₄ O ₁₃ ‧18H ₂ O, chemically pure) and nickel nitrate (Ni(No ₃ ) ₂ ‧18H are weighed ₂ O, chemically pure), formulated into 200 mL of water with water. The solution was added to 50 g of an alumina carrier, immersed at room temperature for 3 hours, and the immersion liquid was ultrasonically treated for 30 minutes during the impregnation, cooled, filtered, and dried in a microwave oven for about 15 minutes. The composition of the catalyst was: 30.0% by weight of WO ₃ , 3.1% by weight of NiO and the balance of alumina.

The conventional catalytic cracking catalysts are MLC-500 and CGP-1, respectively, and their properties are listed in Table 2.

Example 1

In this embodiment, the vacuum residue feedstock oil A is used as a raw material for catalytic cracking, and is tested on a medium-sized device of the riser reactor. The inferior raw material enters the lower portion of the reaction zone I, contacts with the catalyst GZ-1, and reacts in the reaction. In the lower part of Zone 1, the inferior raw materials are subjected to a cracking reaction at a reaction temperature of 600 ° C, a weight hourly space velocity of 100 h ^-1 , a weight ratio of the catalyst to the raw material of 6, and a weight ratio of water vapor to the raw material of 0.05; in the reaction zone II, oil and gas After the mixed propane and C ₄ hydrocarbons and diesel oil are mixed, the cracking reaction is carried out at a reaction temperature of 500 ° C, a weight hourly space velocity of 30 h ^-1 , and a weight ratio of water vapor to the raw material of 0.05, and the oil and gas and the carbon-bearing catalyst are separated in the settler. The product is cut in the separation system according to the distillation range to obtain dry gas, liquefied gas (including propylene, propane and C ₄ hydrocarbons, the same below), gasoline, diesel and catalytic wax oil with a cutting point greater than 330 ° C. 24.48% by weight of feedstock oil and gas oil by catalytic hydrotreatment, a hydrogen partial pressure of 18.0MPa, the reaction temperature is 350 deg.] C, hydrogen hydrotreated oil volume ratio 1500v / v, 1.5h ^-1 LHSV of the reaction conditions, After the catalyst wax into another set of the same medium as described above catalytic cracking apparatus using a catalyst MLC-500, in the reaction zone I, the reaction temperature is 600 ℃, a weight hourly space velocity of 100h ^-1, catalyst to feed weight ratio of 6, In the reaction zone II, the reaction temperature is 500 ° C, the weight hourly space velocity is 20 h ^-1 , the weight ratio of the catalytic cracking catalyst to the raw material is 6, and the dry gas, the liquefied gas, the gasoline, the diesel oil and the catalytic wax oil are separated, and the catalytic wax oil is returned to the hydrogenation treatment. Device. Operating conditions and product distribution are listed in Table 3.

It can be seen from Table 3 that the total liquid yield is as high as 88.39 wt%, wherein the gasoline yield is as high as 51.75 wt%, the propylene yield is as high as 5.05 wt%, and the dry gas yield is only 2.62 wt%, and the slurry yield is only 1.10% by weight.

Comparative Example 1

The comparative example is directly used as a raw material for catalytic cracking of the vacuum residue raw material A, and is tested on a medium riser reactor apparatus at a reaction temperature of 500 ° C and a reaction time of 2.5 seconds. The weight ratio of the catalyst to the raw material is 6, water. The cracking reaction is carried out under the condition that the weight ratio of steam to raw material is 0.05; the oil and gas and the carbon-bearing catalyst are separated in the settler, and the product is cut in the separation system according to the distillation range to obtain dry gas, liquefied gas, gasoline, diesel oil and oil slurry. Operating conditions and product distribution are listed in Table 3.

It can be seen from Table 3 that the total liquid yield is only 77.44% by weight, wherein the gasoline yield is only 43.76% by weight, the propylene yield is only 4.21% by weight, and the dry gas yield is as high as 3.49% by weight. Up to 9.18% by weight. Compared with Example 1, the total liquid yield of the control was greatly reduced, resulting in a decrease in the utilization efficiency of petroleum resources.

Example 2

This embodiment was tested according to the flow of Fig. 2, and the inferior hydrogenated residue raw material C was used as a raw material for catalytic cracking, and was tested on a medium-sized device of the riser reactor. The inferior raw material entered the lower portion of the reaction zone I and was in contact with the catalyst GZ-1. The reaction occurs. In the lower part of the reaction zone I, the inferior raw material is subjected to a cracking reaction at a reaction temperature of 600 ° C, a weight hourly space velocity of 100 h ^-1 , a weight ratio of the catalyst to the raw material of 6, and a weight ratio of water vapor to the raw material of 0.05; In Zone II, the oil and gas are mixed with the cooling regenerated catalyst as the cold shock medium, and then the cracking reaction is carried out at a reaction temperature of 500 ° C, a weight hourly space velocity of 30 h ^-1 , and a weight ratio of water vapor to the raw material of 0.05. The oil and gas and carbon-bearing catalyst are The settler is separated, and the product is cut in the separation system according to the distillation range to obtain dry gas, liquefied gas including propylene, gasoline, diesel oil and catalytic wax oil having a cutting point of more than 330 ° C, and the catalytic wax oil accounts for 38.57% of the weight of the raw material oil. Then, the catalytic wax oil is subjected to hydrogenation treatment, and hydrogen is carried out under the reaction conditions of hydrogen partial pressure of 18.0 MPa, reaction temperature of 350 ° C, hydrogen oil volume ratio of 1500 v/v, and volume space velocity of 1.5 h ^-1 . The hydrogenated catalytic wax oil enters another conventional medium-sized catalytic cracking unit using the catalyst CGP-1 in the reaction zone I, the reaction temperature is 600 ° C, the weight hourly space velocity is 100 h ^-1 , and the catalytic cracking catalyst and the weight of the raw material are used. Ratio 6, water vapor I raw material weight ratio 0.10, in reaction zone II, reaction temperature 500 ° C, heavy hourly space velocity 20 h ^-1 , catalytic cracking catalyst and raw material weight ratio 6, separation of dry gas, liquefied gas, gasoline, diesel And catalyzing the wax oil, catalyzing the return of the wax oil to the hydrotreating unit. Operating conditions and product distribution are listed in Table 4.

It can be seen from Table 4 that the total liquid yield is as high as 87.49 wt%, wherein the gasoline yield is as high as 41.35 wt%, the propylene yield is as high as 8.04 wt%, and the dry gas yield is only 2.68 wt%, and the slurry yield is only 1.30% by weight.

Comparative Example 2

The comparative example was directly used as a raw material for catalytic cracking of inferior hydrogenated residue raw material C, and was tested on a medium riser reactor apparatus using a catalyst CGP-1 at a reaction temperature of 500 ° C and a reaction time of 2.5 seconds. The weight ratio is 6. The cracking reaction is carried out under the condition that the weight ratio of water vapor to the raw material is 0.10; the oil and gas and the carbon-bearing catalyst are separated in the settler, and the product is cut in the separation system according to the distillation range to obtain dry gas, liquefied gas and gasoline. , diesel, oil slurry. Operating conditions and product distribution are listed in Table 4.

As can be seen from Table 4, the total liquid yield is only 77.29% by weight, wherein the gasoline yield is only 33.04% by weight, the propylene yield is only 7.06% by weight, and the dry gas yield is as high as 3.63 weight%, the slurry yield. Up to 9.77% by weight. Compared with Example 2, the total liquid yield of the control was greatly reduced, resulting in a decrease in the utilization efficiency of petroleum resources.

Example 3

This example was tested according to the flow of Figure 2, the high acid crude feed E was used as a raw material for catalytic cracking, and the test was carried out on a medium reactor of the riser reactor. The inferior raw material entered the lower part of the reaction zone I and was in contact with the catalyst GZ-1. The reaction occurs. In the lower part of the reaction zone I, the inferior raw material is subjected to a cracking reaction at a reaction temperature of 600 ° C, a weight hourly space velocity of 100 h ^-1 , a weight ratio of the catalyst to the raw material of 6, and a weight ratio of water vapor to the raw material of 0.05; In Zone II, the oil and gas is subjected to a cracking reaction at a reaction temperature of 500 ° C, a weight hourly space velocity of 30 h ^-1 , and a weight ratio of water vapor to the raw material of 0.05. The oil and gas and carbon-bearing catalyst are separated in a settler, and the product is separated in a separation system. Cutting, thereby obtaining dry gas, liquefied gas including propylene, gasoline, diesel oil and catalytic wax oil having a cutting point of more than 330 ° C, the catalytic wax oil accounts for 18.03% by weight of the raw material oil, and then the catalytic wax oil is hydrotreated, in hydrogen The hydrogenation treatment is carried out under the reaction conditions of partial pressure of 18.0 MPa, reaction temperature of 350 ° C, hydrogen oil volume ratio of 1500 v/v and volumetric space velocity of 1.5 h ^-1 , and the hydrogenated catalytic wax oil enters another conventional set. The medium-sized catalytic cracking unit adopts the catalyst CGP-1 in the reaction zone I, the reaction temperature is 600 ° C, the weight hourly space velocity is 100 h ^-1 , the weight ratio of the catalytic cracking catalyst to the raw material is 6, and the weight ratio of the water vapor/feedstock is 0.10. Zone II, the reaction temperature is 500 ° C, the weight hourly space velocity is 20 h ^-1 , and the weight ratio of the catalytic cracking catalyst to the raw material is 6, and the dry gas, the liquefied gas, the gasoline, the diesel oil and the catalytic wax oil are separated, and the catalytic wax oil is returned to the hydrogenation treatment device. Operating conditions and product distribution are listed in Table 5.

As can be seen from Table 5, the total liquid yield was as high as 87.51% by weight, wherein the gasoline yield was as high as 40.17 wt%, the propylene yield was as high as 7.57 wt%, and the dry gas yield was only 3.21 wt%.

Comparative Example 3

The comparative example was directly used as a raw material for catalytic cracking of high-acid crude oil raw material E, and was tested on a medium-sized riser reactor apparatus using a catalyst CGP-1 at a reaction temperature of 500 ° C and a reaction time of 2.5 seconds. The weight ratio is 6. The cracking reaction is carried out under the condition that the weight ratio of water vapor to the raw material is 0.10; the oil and gas and the carbon-bearing catalyst are separated in the settler, and the product is cut in the separation system according to the distillation range to obtain dry gas, liquefied gas, gasoline, Diesel, oil slurry. Operating conditions and product distribution are listed in Table 5.

It can be seen from Table 5 that the total liquid yield is only 77.29% by weight, wherein the gasoline yield is only 35.43% by weight, the propylene yield is only 6.52% by weight, and the dry gas yield is as high as 5.51% by weight. Up to 6.22% by weight. Compared with Example 3, the total liquid yield of the control was greatly reduced, resulting in a decrease in the utilization efficiency of petroleum resources.

Example 4~5

This embodiment is tested according to the flow of FIG. 2, and the atmospheric residue B and the high acid value crude oil D are respectively used as raw materials for catalytic cracking, and are tested on a medium-sized device of the riser reactor, and the inferior raw materials enter the lower portion of the reaction zone I. Contact with catalyst GZ-1 and react. In the lower part of reaction zone I, the inferior raw material has a reaction temperature of 600 ° C, a weight hourly space velocity of 100 h ^-1 , a weight ratio of catalyst to raw material of 6, and a weight ratio of water vapor to raw material of 0.05. The cracking reaction is carried out; in the reaction zone II, the oil and gas is subjected to a cracking reaction at a reaction temperature of 500 ° C, a weight hourly space velocity of 30 h ^-1 , and a weight ratio of water vapor to a raw material of 0.05, and the oil and gas and the carbon-bearing catalyst are separated in a settler. The product is cut in the separation system according to the distillation range to obtain dry gas, liquefied gas including propylene, gasoline, diesel oil and catalytic wax oil having a cutting point of more than 330 ° C, and the catalytic wax oil accounts for 41.90% and 34.13% of the weight of the raw material oil, respectively. after the wax was then catalytic hydrogenation treatment, a hydrogen partial pressure of 18.0MPa, the reaction temperature is 350 deg.] C, hydrogen hydrotreated oil volume ratio 2000v / v, 1.5h ^-1 LHSV of the reaction conditions, the hydrogenation Catalytic gas oil catalytic cracking into the traditional medium apparatus, using the catalyst MLC-500, in the reaction zone I, the reaction temperature is 600 ℃, a weight hourly space velocity of 100h ^-1, the weight ratio of catalyst to feedstock of 6 weight steam / feed ratio of 0.05 In the reaction zone II, the reaction temperature is 500 ° C, the weight hourly space velocity is 20 h ^-1 , the weight ratio of the catalyst to the raw material is 6, and the dry gas, the liquefied gas, the gasoline, the diesel oil and the catalytic wax oil are separated, and the catalytic wax oil is returned to the hydrogenation treatment device. . Operating conditions and product distribution are listed in Table 6.

It can be seen from Table 6 that the total liquid yield is as high as 86.02% by weight and 85.44% by weight, respectively, wherein the gasoline yield is as high as 41.63 wt% and 45.76 wt%, respectively, and the propylene yield is as high as 5.05 wt% and 4.21 wt%, respectively. The gas yields were only 2.89 wt% and 3.03 wt%, respectively, and the oil slurry yields were only 2.30 wt% and 2.18 wt%, respectively.

Example 6

This example was tested according to the flow of Fig. 3, and the vacuum residue raw material A was used as a raw material for catalytic cracking, and was tested on a medium-sized device of the riser reactor. The inferior raw material entered the lower portion of the reaction zone I and was in contact with the catalyst GZ-1. The reaction occurs. In the lower part of the reaction zone I, the inferior raw material is subjected to a cracking reaction at a reaction temperature of 600 ° C, a weight hourly space velocity of 100 h ^-1 , a weight ratio of the catalyst to the raw material of 6, and a weight ratio of water vapor to the raw material of 0.05; Zone II, oil and gas mixed with circulating propane and C ₄ hydrocarbons and diesel oil, the cracking reaction is carried out at a reaction temperature of 500 ° C, a weight hourly space velocity of 30 h ^-1 , and a weight ratio of water vapor to the raw material of 0.05. The oil and gas and carbon-bearing catalyst In the settler separation, the product is cut in the separation system according to the distillation range to obtain dry gas, liquefied gas (including propylene, propane and C ₄ hydrocarbons, the same below), gasoline, diesel and catalytic wax oil with a cutting point greater than 330 ° C. The catalytic wax oil accounts for 24.48% of the weight of the raw material, the catalytic wax oil is extracted by aromatics, the furfural ratio is 2 (v/v) with the catalytic wax oil, the extraction temperature is 75 ° C, the oil is extracted as a chemical raw material, and the raffinate oil is recycled back. Said medium-sized catalytic cracking apparatus. Operating conditions and product distribution are listed in Table 7.

It can be seen from Table 7 that the total liquid yield is as high as 82.01% by weight, wherein the gasoline yield is as high as 47.69% by weight, the propylene yield is as high as 4.86 wt%, and the dry gas yield is only 2.48 wt%, and the slurry yield is only 1.04% by weight, in addition to 7.06% by weight of aromatics-rich chemical materials.

Comparative Example 4

The comparative example is directly used as a raw material for catalytic cracking of the vacuum residue raw material A, and is tested on a medium riser reactor apparatus at a reaction temperature of 500 ° C and a reaction time of 2.5 seconds. The weight ratio of the catalyst to the raw material is 6, water. The cracking reaction is carried out under the condition that the weight ratio of steam to raw material is 0.05; the oil and gas and the carbon-bearing catalyst are separated in the settler, and the product is cut in the separation system according to the distillation range to obtain dry gas, liquefied gas, gasoline, diesel oil and oil slurry. Operating conditions and product distribution are listed in Table 7.

It can be seen from Table 7 that the total liquid yield is only 77.44% by weight, wherein the gasoline yield is only 43.76% by weight, the propylene yield is only 4.21% by weight, and the dry gas yield is as high as 3.49% by weight. Up to 9.18% by weight. Compared with Example 6, the total liquid yield of the control was greatly reduced, resulting in a decrease in the utilization efficiency of petroleum resources.

Example 7

This example was tested according to the flow of Fig. 4, and the inferior hydrogenated residue raw material C was used as a raw material for catalytic cracking, and was tested on a medium-sized device of the riser reactor. The inferior raw material entered the lower portion of the reaction zone I and was in contact with the catalyst GZ-1. The reaction occurs. In the lower part of the reaction zone I, the inferior raw material is subjected to a cracking reaction at a reaction temperature of 600 ° C, a weight hourly space velocity of 100 h ^-1 , a weight ratio of the catalyst to the raw material of 6, and a weight ratio of water vapor to the raw material of 0.05; In Zone II, the oil and gas are mixed with the cooling regenerated catalyst as the cold shock medium, and then the cracking reaction is carried out at a reaction temperature of 500 ° C, a weight hourly space velocity of 30 h ^-1 , and a weight ratio of water vapor to the raw material of 0.05. The oil and gas and carbon-bearing catalyst are The settler is separated, and the product is cut in the separation system according to the distillation range to obtain dry gas, liquefied gas including propylene, gasoline, diesel oil and catalytic wax oil having a cutting point of more than 330 ° C, and the catalytic wax oil accounts for 38.57% of the weight of the raw material oil. Then, the wax oil is extracted by aromatics, the ratio of furfural to catalytic wax oil is 2 (v/v), the temperature of the extraction section is 75 ° C, the oil is extracted as a chemical raw material, and the raffinate oil is introduced into another Medium conventional catalytic cracking apparatus using a catalyst CGP-1, in a reaction zone I, the reaction temperature is 600 ℃, a weight hourly space velocity of 100h ^-1, the catalytic cracking catalyst to feed weight ratio of 6, weight steam / feed ratio of 0.10, in Reaction zone II, reaction temperature 500 ° C, weight hourly space velocity 20 h ^-1 , weight ratio of catalytic cracking catalyst to raw material 6, separation of dry gas, liquefied gas, gasoline, diesel and catalytic wax oil, catalytic wax oil return to aromatics extraction device . Operating conditions and product distribution are listed in Table 8.

It can be seen from Table 8 that the total liquid yield is as high as 81.17 wt%, wherein the gasoline yield is as high as 38.03 wt%, the propylene yield is as high as 7.64 wt%, and the dry gas yield is only 2.51 wt%, and the slurry yield is only 1.23% by weight, in addition to 7.09% by weight of aromatics-rich chemical raw materials.

Comparative Example 5

The comparative example was directly used as a raw material for catalytic cracking of inferior hydrogenated residue raw material C, and was tested on a medium riser reactor apparatus using a catalyst CGP-1 at a reaction temperature of 500 ° C and a reaction time of 2.5 seconds. The weight ratio is 6. The cracking reaction is carried out under the condition that the weight ratio of water vapor to the raw material is 0.10; the oil and gas and the carbon-bearing catalyst are separated in the settler, and the product is cut in the separation system according to the distillation range to obtain dry gas, liquefied gas and gasoline. , diesel, oil slurry. Operating conditions and product distribution are listed in Table 8.

It can be seen from Table 8 that the total liquid yield is only 77.29% by weight, wherein the gasoline yield is only 33.04% by weight, the propylene yield is only 7.06% by weight, and the dry gas yield is as high as 3.63% by weight. Up to 9.77% by weight. Compared with Example 7, the total liquid yield of the control was greatly reduced, resulting in a decrease in the utilization efficiency of petroleum resources.

Example 8

This example was tested according to the flow of Fig. 4, and the high acid crude material E was used as a raw material for catalytic cracking, and was tested on a medium-sized device of the riser reactor. The inferior raw material entered the lower portion of the reaction zone I and was in contact with the catalyst GZ-1. The reaction occurs. In the lower part of the reaction zone I, the inferior raw material is subjected to a cracking reaction at a reaction temperature of 600 ° C, a weight hourly space velocity of 100 h ^-1 , a weight ratio of the catalyst to the raw material of 6, and a weight ratio of water vapor to the raw material of 0.05; In Zone II, the oil and gas is subjected to a cracking reaction at a reaction temperature of 500 ° C, a weight hourly space velocity of 30 h ^-1 , and a weight ratio of water vapor to the raw material of 0.05. The oil and gas and carbon-bearing catalyst are separated in a settler, and the product is separated in a separation system. Cutting, thereby obtaining dry gas, liquefied gas including propylene, gasoline, diesel oil and catalytic wax oil having a cutting point of more than 330 ° C, the catalytic wax oil accounting for 18.03% by weight of the raw material oil, and then catalyzing the extraction of wax oil by aromatic hydrocarbon, furfural and The catalytic wax-to-oil ratio is 2 (v/v), the extraction section temperature is 75 ° C, the oil is extracted as a chemical raw material, and the raffinate oil enters another conventional medium-sized catalytic cracking unit using the catalyst CGP- 1, in reaction zone I, reaction temperature 600 ° C, weight hourly space velocity 100 h ^-1 , weight ratio of catalytic cracking catalyst to raw material 6, water vapor / raw material weight ratio 0.10, in reaction zone II, reaction temperature 500 ° C, heavy time and space The speed is 20h ^-1 , and the weight ratio of the catalytic cracking catalyst to the raw material is 6, and the dry gas, the liquefied gas, the gasoline, the diesel oil and the catalytic wax oil are separated, and the catalytic wax oil is returned to the aromatic hydrocarbon extraction device. Operating conditions and product distribution are listed in Table 9.

It can be seen from Table 9 that the total liquid yield is as high as 81.19% by weight, wherein the gasoline yield is as high as 36.93 wt%, the propylene yield is as high as 7.20 wt%, and the dry gas yield is only 3.01 wt%, and the other is 7.08 wt%. Chemical raw materials rich in aromatics.

Comparative Example 6

The comparative example was directly used as a raw material for catalytic cracking of high-acid crude oil raw material E, and was tested on a medium-sized riser reactor apparatus using a catalyst CGP-1 at a reaction temperature of 500 ° C and a reaction time of 2.5 seconds. The weight ratio is 6. The cracking reaction is carried out under the condition that the weight ratio of water vapor to the raw material is 0.10; the oil and gas and the carbon-bearing catalyst are separated in the settler, and the product is cut in the separation system according to the distillation range to obtain dry gas, liquefied gas, gasoline, Diesel, oil slurry. Operating conditions and product distribution are listed in Table 9.

It can be seen from Table 9 that the total liquid yield is only 77.29% by weight, wherein the gasoline yield is only 35.43% by weight, the propylene yield is only 6.52% by weight, and the dry gas yield is as high as 5.51% by weight. Up to 6.22% by weight. Compared with Example 8, the total liquid yield of the control was greatly reduced, resulting in a decrease in the utilization efficiency of petroleum resources.

Example 9~10

This embodiment is tested according to the flow of FIG. 4, and the atmospheric residue B and the high acid value crude oil D are respectively used as raw materials for catalytic cracking, and are tested on a medium-sized device of the riser reactor, and the inferior raw materials enter the lower portion of the reaction zone I. Contact with catalyst GZ-1 and react. In the lower part of reaction zone I, the inferior raw material has a reaction temperature of 600 ° C, a weight hourly space velocity of 100 h ^-1 , a weight ratio of catalyst to raw material of 6, and a weight ratio of water vapor to raw material of 0.05. The cracking reaction is carried out; in the reaction zone II, the oil and gas is subjected to a cracking reaction at a reaction temperature of 500 ° C, a weight hourly space velocity of 30 h ^-1 , and a weight ratio of water vapor to a raw material of 0.05, and the oil and gas and the carbon-bearing catalyst are separated in a settler. The product is cut in the separation system according to the distillation range to obtain dry gas, liquefied gas including propylene, gasoline, diesel oil and catalytic wax oil having a cutting point of more than 330 ° C, and the catalytic wax oil accounts for 41.90% and 34.13% of the weight of the raw material oil, respectively. Then, the wax oil is extracted by aromatics, the ratio of furfural to catalytic wax oil is 2 (v/v), the temperature of the extraction section is 75 ° C, the oil is extracted as a chemical raw material, and the raffinate oil enters another traditional medium-sized catalyst. The cracking device adopts the catalyst MLC-500, in the reaction zone I, the reaction temperature is 600 ° C, the weight hourly space velocity is 100 h ^-1 , the weight ratio of the catalyst to the raw material is 6, the weight ratio of the steam to the raw material is 0.05, in the reaction zone II, the reaction temperature 500 ° C, heavy hourly space velocity 20 h ^-1 , the weight ratio of catalyst to raw material 6, separation of dry gas, liquefied gas, gasoline, diesel and catalytic wax oil, catalytic wax oil back to the aromatics extraction device. Operating conditions and product distribution are listed in Table 10.

It can be seen from Table 10 that the total liquid yield is as high as 78.76 wt% and 78.24 wt%, respectively, wherein the gasoline yield is as high as 37.73 wt% and 41.52 wt%, respectively, and the propylene yield is as high as 4.82 wt% and 4.05 wt%, respectively. The gas yields were only 2.69 wt% and 2.81 wt%, respectively, and the oil slurry yields were only 2.14 wt% and 2.01 wt%, respectively, and 8.26 wt% and 8.23 wt% of aromatic hydrocarbon-rich chemical materials were obtained, respectively.

All of the above references are incorporated herein by reference for all useful purposes.

While the invention has been shown and described with respect to the specific embodiments of the embodiments of the present invention It is limited to the specific form illustrated herein.

I, II. . . Reaction zone

1, 3~7, 11, 14~17, 19~30. . . Pipeline

2. . . reactor

8. . . Settler

9. . . Gas collection room

10. . . Stripping section

12. . . Inclined tube

13. . . Regenerator

18. . . Separation system

31. . . Conversion device

32. . . Processing unit

1 is a schematic view showing the flow of a work process according to a first embodiment of the present invention.

2 is a schematic view showing the flow of a work process according to a second embodiment of the present invention.

3 is a schematic view showing the flow of a work process according to a third embodiment of the present invention.

4 is a schematic view showing the flow of a work process according to a fourth embodiment of the present invention.

I, II. . . Reaction zone

1, 3~7, 11, 14~17, 19~30. . . Pipeline

2. . . reactor

8. . . Settler

9. . . Gas collection room

10. . . Stripping section

12. . . Inclined tube

13. . . Regenerator

18. . . Separation system

32. . . Processing unit

Claims (21)

A method for preparing light fuel oil from inferior feedstock oil, characterized in that the method comprises the following steps: (1) preheating inferior feedstock oil enters a first reaction zone of a catalytic converter reactor and is contacted with a hot catalytic converter catalyst The cracking reaction occurs, and the generated oil and gas and the used catalyst are optionally mixed with the light feedstock oil and/or the cold shock medium and then enter the second reaction zone of the catalytic conversion reactor for further cracking reaction, hydrogen transfer reaction and isomerization. After the reaction, the reaction product and the carbon-containing catalyst to be reacted after gas-solid separation, the reaction product enters the separation system and is separated into dry gas, liquefied gas, gasoline, diesel oil and catalytic wax oil, optionally, the catalyst to be produced is passed through water. The steam is stripped and sent to the regenerator for charring regeneration, and the hot regenerated catalyst is returned to the reactor for recycling; wherein the reaction conditions of the first reaction zone and the second reaction zone are characterized by sufficient reaction to obtain the feedstock 12%% to 60% by weight of the catalytic wax oil product; (2), the catalytic wax oil enters the hydrogenation treatment device or/and the aromatic hydrocarbon extraction device to obtain hydrogenated catalytic wax oil or/and extraction Residual oil; (3), the hydrogenation catalytic wax oil or / and raffinate oil is recycled to the first reaction zone of the step (1) catalytic conversion reactor or / and other catalytic converters to further react to obtain the desired product light fuel oil . The method of claim 1, wherein the inferior feedstock oil is heavy petroleum hydrocarbon and/or other mineral oil, wherein the heavy petroleum hydrocarbon is selected from the group consisting of vacuum residue, inferior atmospheric residue, and inferior hydrogenated slag. a mixture of one or more of oil, coker gas oil, deasphalted oil, high acid value crude oil, and high metal crude oil; other mineral oils are one of coal liquefied oil, oil sand oil, and shale oil Or more. The method of claim 1, wherein the inferior feedstock has a property satisfying at least one of the following indexes: a density of 900 to 1000 kg/ ^m3 , a residual carbon of 4 to 15% by weight, and a metal content of 15 to 600 ppm, and an acid value of 0.5 to 20 mg KOH/g. The method of claim 3, wherein the inferior feedstock has a property satisfying at least one of the following indexes: a density of 930 to 960 kg/ ^m3 , a residual carbon of 6 to 12% by weight, and a metal content of 15 to 100 ppm, and an acid value of 0.5 to 10 mg KOH/g. The method of claim 1, wherein the first reaction zone and the second reaction zone reaction conditions are sufficient to cause the reaction to comprise a catalytic wax oil product comprising from 20% to 40% by weight of the feedstock oil. The method of claim 1, wherein the light feedstock oil is selected from one or more of the group consisting of liquefied gas, gasoline, and diesel. The method of claim 1, wherein the cold shock medium is any ratio of one or more selected from the group consisting of a cold shock, a cooled regenerated catalyst, a cooled semi-regenerated catalyst, a spent catalyst, and a fresh catalyst. a mixture wherein the cold shock agent is a mixture of one or more selected from the group consisting of liquefied gas, naphtha, stabilized gasoline, diesel, heavy diesel or water; the cooled regenerated catalyst and the cooled semi-regenerated catalyst are awaiting The catalyst was obtained by two-stage regeneration and one-stage regeneration and cooling. The method of claim 1, wherein the catalytic conversion catalyst comprises a zeolite, an inorganic oxide and optionally a clay, and each component comprises a total weight of the catalyst: 1% by weight to 50% by weight of the zeolite, and the inorganic oxide 5 Weight % - 99% by weight, clay 0% by weight - 70% by weight, wherein the zeolite as an active component is a medium pore zeolite and / or optionally a large pore zeolite selected from the group consisting of ZSM series zeolites and / or ZRP zeolites The macroporous zeolite is selected from the group consisting of one or more of the group consisting of rare earth Y, rare earth hydrogen Y, ultrastable Y, and sorghum Y. For example, in the method of claim 1, wherein the conditions of the first reaction zone include: a reaction temperature of 510 ° C to 650 ° C, a weight hourly space velocity of 10 to 200 h ^-1 , and a weight ratio of the catalyst to the feedstock oil of 3 to 15: 1. The weight ratio of water vapor to feedstock oil is 0.03~0.3:1, and the pressure is 130kPa~450kPa. The method of claim 9, wherein the conditions of the first reaction zone include: a reaction temperature of 520 ° C to 600 ° C, a weight hourly space velocity of 15 to 150 h ^-1 , and a weight ratio of the catalyst to the feedstock oil of 4 to 12: 1. The weight ratio of water vapor to feedstock oil is 0.05~0.2:1, and the pressure is 130kPa~450kPa. For example, in the method of claim 1, wherein the conditions of the second reaction zone include: a reaction temperature of 420 ° C to 550 ° C and a weight hourly space velocity of 5 to 150 h ^-1 . For example, in the method of claim 11, wherein the conditions of the second reaction zone include: a reaction temperature of 460 ° C to 530 ° C and a weight hourly space velocity of 15 to 80 h ^-1 . The method of claim 1, wherein at least one of propane and C ₄ hydrocarbons in the liquefied gas, and diesel fuel, enters the second reaction zone as a light feedstock oil. The method of claim 1, wherein the solvent for extracting the aromatic hydrocarbon is selected from one of furfural, dimethyl hydrazine, dimethylformamide, monoethanolamine, ethylene glycol, and 1,2-propanediol. A variety of extraction temperatures of 40 to 120. C, the volume ratio of the solvent to the catalytic wax oil is 0.5 to 5.0:1. The method of claim 1, wherein the hydrogenation treatment is in contact with a hydrogenation catalyst in the presence of hydrogen, at a hydrogen partial pressure of 3.0 to 20.0 MPa, a reaction temperature of 300 to 450 ° C, and a hydrogen oil volume ratio of 300 to 2000 volts. /v, hydrogenation treatment under the reaction conditions of a volume space velocity of 0.1 to 3.0 h ^-1 . The method of claim 1, wherein the catalytic wax oil has a cutting temperature of not less than 250 ° C and a hydrogen content of not less than 10.5% by weight. The method of claim 16, wherein the catalytic wax oil has a cutting temperature of not lower than 330 ° C, and the hydrogen content is not less than 10.8 wt%. The method of claim 8, wherein the medium pore zeolite comprises from 0% by weight to 50% by weight based on the total weight of the zeolite. The method of claim 18, wherein the medium pore zeolite comprises from 0% by weight to 20% by weight based on the total weight of the zeolite. The method of claim 1, wherein the reactor is selected from the group consisting of a riser, a linear velocity fluidized bed, a fluidized bed of equal diameter, an upstream conveyor line, and a downstream conveyor line. Combinations of two or more of the same reactor, including in series or / and in parallel, wherein the riser is a conventional equal diameter riser or a riser of various forms. The method of claim 20, wherein the riser is a variable diameter riser reactor.