CN110317630B - Catalyst zoned catalytic cracking method and device - Google Patents

Abstract

The present invention provides a method and a device for catalytic cracking by catalyst zone. The device comprises a main reactor (3), a secondary reactor (11), a regenerator (14), an A catalyst pre-rotation separator (19) and a B catalyst storage tank (22), and the interior of the B catalyst storage tank (22) The upper part is provided with a B catalyst initial swirl separator (20), the regenerator (14) is connected with the main reactor (3) and the A catalyst initial swirl separator (19) through pipelines respectively, and the top of the A catalyst initial swirl separator (19) is connected It is connected to the B catalyst primary cyclone separator (20) through pipelines, and the bottom is connected to the regenerator (14) through pipelines. The top of the B catalyst primary cyclone separator (20) is connected to the regenerator (14) through pipelines. The bottom of the catalyst primary cyclone separator (20) is provided with an opening communicating with the inner cavity of the B catalyst storage tank (22), and the bottom of the B catalyst storage tank (22) is connected to the secondary reactor (11) through a pipeline.

Description

A kind of catalyst zone catalytic cracking method and device

technical field

The present invention relates to the field of petrochemical industry, in particular, the present invention relates to a method and a device for catalytic cracking of catalyst zones.

Background technique

Catalytic cracking process is the core process in oil refining technology. It is not only the main means of heavy oil processing and the main source of light oil components, but also has an irreplaceable position in providing light olefins and petrochemical integration technology.

Catalytic cracking is a typical parallel sequential reaction, including a primary reaction and a secondary reaction. Among them, the primary reaction is mainly the cracking reaction of heavy components to generate light hydrocarbons and olefin products, and the secondary reaction is mainly the cracking of light hydrocarbons and further reactions of olefins, such as Continuous cracking of gasoline and diesel fractions and hydrogen transfer reaction of olefin, isomerization reaction, alkylation reaction, etc. It is found that the process conditions and catalyst properties required for the primary reaction and the secondary reaction in catalytic cracking are quite different. The thermodynamic results show that the cracking of macromolecular heavy oil requires lower activation energy, while the cracking of smaller molecules (gasoline) requires higher activation energy, so the primary cracking of heavy oil requires lower temperature, while the secondary cracking products such as gasoline Cracking should be carried out at a higher temperature, and at the same time, the secondary reaction requires a longer reaction time. In order to take into account the different requirements of the primary reaction and the secondary reaction on the reaction temperature and reaction time, the catalytic cracking zone control process technology has been developed. Different thermodynamic properties of secondary reactions. Such as DCC-plus process. The DCC-plus process adopts the form of riser reactor + fluidized bed reactor, and uses the riser reactor and the fluidized bed reactor in series to realize the different requirements for the reaction time of the primary reaction and the secondary reaction. The technology of replenishing the regenerated catalyst with heat inside the fluidized bed reactor realizes zone control, changes the catalyst activity distribution and reaction temperature of the fluidized bed reactor, and at the same time, it can reduce the increase of the fluidized bed reactor while keeping the temperature of the fluidized bed reactor constant. The temperature of the tube reactor and the ratio of agent to oil can meet the respective requirements of the catalyst activity and reaction conditions for the primary cracking reaction of heavy feedstocks and the secondary cracking reaction of light feedstocks. The results show that the use of the riser reactor in series with the fluidized bed reactor and supplementing the regenerated catalyst to the fluidized bed reactor can change the residence time of oil and gas in different reaction zones, increase the cracking of heavy oil, improve the yield of light olefins and Improving gasoline properties and reducing the riser outlet temperature and the riser inlet oil mixing temperature can significantly reduce the dry gas and coke yields.

CN201610917106.7 discloses a catalytic cracking method for producing low-carbon olefins and light aromatic hydrocarbons. The heavy raw materials are contacted and reacted with the first part of the catalytic cracking catalyst in the first reactor (riser reactor I). The light feedstock and the light feedstock rich in olefins are reacted in the second reactor (riser reactor II) and the third reactor (fluidized bed reactor) in contact with the second part of the catalytic cracking catalyst to increase the production of light olefins and light aromatics. In this method, three reactors are set up, which are equivalent to three reaction zones, and the zone cracking conversion of raw materials is realized, but the same catalyst is used, although the first reactor and the second reactor both use the regenerated catalyst However, there is no matching of different catalysts for the difference in the conversion properties of the raw materials, and the partition of the catalysts is not realized, and the raw materials, catalysts and process conditions cannot be highly matched. CN98101765.7 discloses a method for simultaneously producing low-carbon olefins and high-aromatic gasoline, so that heavy petroleum hydrocarbons and water vapor are placed in the lower part of a composite reactor composed of a riser and a dense-phase fluidized bed, that is, the lower part of the riser Contact with the zeolite-containing catalyst, so that the light petroleum hydrocarbons enter the upper part of the composite reactor, that is, the bottom of the dense-phase fluidized bed, to contact the zeolite-containing catalyst from the riser. In this method, two reaction zones are set to realize the zone cracking conversion of raw materials, but a catalyst is used, and the catalyst of the second reaction zone (dense phase fluidized bed) is from the first reaction zone (riser reactor). ) catalyst, the partition of the catalyst is not realized, and the catalyst activity and the conversion performance of the catalyst and the raw material cannot be highly matched.

In addition, catalytic cracking is a monomolecular endothermic reaction that occurs at strong acid sites, while hydrogen transfer reaction is a bimolecular exothermic reaction that occurs at weak acid sites and requires higher acid density. Isomerization is unimolecular exothermic and occurs at stronger acid sites. Moreover, with different pore sizes of catalysts, there are also differences in isomerization performance. For example, as the pore size of zeolite decreases, the isomerization performance of zeolite gradually decreases. After Y molecular sieve is modified with rare earth or phosphorus, the isomerization performance of Y molecular sieve is enhanced. The cracking of heavy oil macromolecules requires a larger catalyst pore size, while the cracking of light oil small molecules requires a smaller catalyst pore size. For the same catalyst, it is difficult to take into account the above-mentioned properties at the same time, and it is often overlooked. In order to make up for the defect that the same catalyst cannot take into account multiple properties, the current practice is to use two catalysts, such as the mixed use of USY and ZSM series catalysts, by adding ZSM series catalysts to enhance the secondary reaction of small molecules to increase the production of low carbon Olefins. CN200410006189.1 discloses a chemical type oil refining method for producing light olefins and aromatics, wherein the catalytic cracking catalyst is a mixture of mesoporous ZSM series catalysts and macroporous Y series catalysts. The problem is that the primary cracking and condensation reaction of heavy oil It can also occur on the surface of the ZSM series catalyst, so that the surface of the ZSM series catalyst and the entrance of the pores are covered with coke, which prevents small molecules from entering the pores of the ZSM series catalyst to continue the reaction, which seriously reduces the catalytic activity of the ZSM series. The last second reaction was less.

SUMMARY OF THE INVENTION

In order to solve the above problems, the present invention proposes a catalytic cracking method and device of catalyst partition, using two catalysts with different properties to meet the requirement that the same catalyst cannot take into account multiple performances. At the same time, the two regenerated catalysts are separated and enriched through the catalyst pre-cyclone separator, and then the two catalysts are transported to different reaction zones, where different raw materials are matched in each reaction zone, and different process conditions are matched according to the thermodynamic properties. In order to achieve a high degree of matching between the catalyst, the raw materials and the process conditions, the catalytic performance of each catalyst is strengthened, so that the catalytic performance of the catalyst can be fully utilized. It avoids the influence of one catalyst on the other when the catalysts are mixed.

An object of the present invention is to provide a catalyst zone catalytic cracking device;

Another object of the present invention is to provide a catalyst zone catalytic cracking method.

In order to achieve the above object, on the one hand, the present invention provides a catalyst zoned catalytic cracking device, wherein the device includes a main reactor 3 for catalytic cracking of heavy feedstock oil, a catalytic cracking reaction for light feedstock oil. The secondary reactor 11, the regenerator 14, the A catalyst primary cyclone separator 19 and the B catalyst storage tank 22, the B catalyst primary cyclone separator 20 is arranged above the B catalyst storage tank 22, and the regenerator 14 is connected to the main reactor through pipelines respectively. The device 3 is connected with the A catalyst preliminary spin separator 19, the top of the A catalyst preliminary spin separator 19 is connected with the B catalyst preliminary spin separator 20 through the pipeline, and the bottom is connected with the regenerator 14 through the pipeline, and the B catalyst preliminary spin separator The top of the catalyst 20 is connected to the regenerator 14 through a pipeline, the bottom of the B catalyst primary cyclone separator 20 is provided with an opening communicating with the inner cavity of the B catalyst storage tank 22, and the bottom of the B catalyst storage tank 22 is connected to the secondary reactor 11 through a pipeline.

According to some specific embodiments of the present invention, the types of the main reactor and the auxiliary reactor are respectively independent riser reactor, transport bed reactor, riser+fast bed reactor, turbulent bed+fast bed reaction A combination of one or more of the devices.

The catalyst primary cyclone separator is a cyclone separator used for the preliminary separation of the catalyst. The cyclone separator is a known product and is a common separation equipment in the chemical industry.

According to some specific embodiments of the present invention, the primary cyclone separator of the A catalyst is a cyclone separator capable of separating 50-100 wt% of the A catalyst, and the air inlet is opened at the upper or middle position. Those skilled in the art can select a suitable size of the primary spin separator according to the separation index described in the present invention.

The parameters of catalyst A are: catalyst bulk density is 0.8-1.5g/cm ³ , preferably 0.9-1.2g/cm ³ ; average particle size is 80-140 μm, preferably 90-120 μm; particle size distribution: larger than 80 μm particle size The particles of the catalyst A account for 60-100wt% of the total weight of catalyst A, preferably 80-100wt%

According to some specific embodiments of the present invention, wherein, the B catalyst primary cyclone separator is a cyclone separator capable of achieving 50-100 wt% separation of the B catalyst, and the air inlet is opened at the upper or middle position.

The parameters of catalyst B are: catalyst bulk density is 0.4-0.7g/cm ³ , preferably 0.5-0.65g/cm ³ ; average particle size is 20-80 μm, preferably 40-60 μm; particle size distribution: 30-50 μm particles The diameter of the particles accounts for 60-100 wt % of the total weight of the catalyst B, preferably 80-100 wt %.

According to some specific embodiments of the present invention, wherein, the regenerator 14 is connected to the bottom of the regenerated catalyst standpipe 18 through the first regeneration inclined pipe 16, and the top of the regenerated catalyst standpipe 18 is connected to the A catalyst primary spin separator 19; The bottom of the cyclone separator 19 is connected with the regenerator 14 through the A catalyst conveying pipe 21; the bottom of the B catalyst storage tank 22 is connected with the secondary reactor 11 through the second regeneration inclined pipe 24; the regenerator 14 is connected with the main reactor through the third regeneration inclined pipe 25. device 3 is connected.

According to some specific embodiments of the present invention, the main reactor 3 and the secondary reactor 11 are respectively riser reactors; the top of the main reactor 3 is connected to the bottom of the stripper 4 and enters the settler through the stripper 4 5. The top of the stripper 4 is connected with the bottom of the settler 5, and the top of the secondary reactor 11 is connected with the settler 5; the bottom of the main reactor 3 is connected with the regenerator 14 through the third regeneration inclined pipe 25; The second regeneration inclined pipe 24 is connected to the bottom of the B catalyst storage tank 22;

According to some specific embodiments of the present invention, a first primary cyclone separator 12 is arranged in the settler 5 , and the top of the secondary reactor 11 is connected to the first primary cyclone separator 12 .

According to some specific embodiments of the present invention, a second primary cyclone separator 6 connected to the main reactor 3 is also arranged in the settler 5, and a secondary cyclone 7 is arranged on the top of the settler 5. The secondary cyclone separator The top of 7 communicates with the outside world through the top of settler 5.

According to some specific embodiments of the present invention, a cyclone separator 27 is arranged in the upper part of the regenerator 14 , and the top of the cyclone separator 27 communicates with the outside world through a pipeline passing through the top of the regenerator 14 .

The above-mentioned catalytic cracking reaction unit adds a set of catalyst initial spin separation system to the original DCC-plus unit, which is used for the separation and enrichment of A and B catalysts, and partitions A and B catalysts into the main and secondary reactors, and matches them. For raw materials with large differences in cracking properties, the primary cyclone separation system consists of two cyclone or coarse cyclone or cyclone heads in series, and also includes a B catalyst storage tank and a catalyst delivery pipe.

In another aspect, the present invention also provides a catalyst zone catalytic cracking method, wherein the method includes using two different catalysts in the catalytic cracking reaction of petroleum hydrocarbons, including using A catalyst in the catalytic cracking reaction of heavy feedstock oil , and use B catalyst in light feedstock catalytic cracking reaction.

According to some specific embodiments of the present invention, wherein, catalyst A has a bulk density of 0.8-1.5 g/cm ³ , an average particle size of 80-140 μm, and particle size distribution: particles with a particle size larger than 80 μm account for 60-100 wt % of the total weight of catalyst A .

According to some specific embodiments of the present invention, wherein the A catalyst has a bulk density of 0.9-1.2 g/cm ³ .

According to some specific embodiments of the present invention, the A catalyst has an average particle size of 90-120 μm.

According to some specific embodiments of the present invention, wherein, the particle size distribution of the catalyst A: particles with a particle size larger than 80 μm account for 80-100 wt % of the total weight of the catalyst A. According to some specific embodiments of the present invention, the bulk density of catalyst B is 0.4-0.7 g/cm ³ , the average particle size is 20-80 μm, and the particle size distribution: particles with a particle size of 30-50 μm account for 60-100 wt of the total weight of catalyst B %.

According to some specific embodiments of the present invention, the bulk density of the B catalyst is 0.5-0.65 g/cm ³ .

According to some specific embodiments of the present invention, the average particle size of the B catalyst is 40-60 μm.

A catalyst has high heavy feedstock cracking performance and high matrix cracking activity; B catalyst has high olefin selectivity, low hydrogen transfer activity, and strong secondary conversion capacity of light oil.

The A catalyst used in the present invention can be any catalyst suitable for catalytic cracking of heavy feedstocks.

According to some specific embodiments of the present invention, wherein, the catalyst A comprises the following components by weight percentage: 15-40% of natural minerals, 10-35% of ZSM-5 molecular sieve or modified ZSM-5 molecular sieve, 50- 75% Y-type molecular sieve.

The natural mineral is selected from at least one of kaolin, halloysite, montmorillonite, diatomite, attapulgite, sepiolite, halloysite, hydrotalcite, bentonite, and rectorite. The Y-type molecular sieve is selected from at least one of DASY molecular sieve, rare earth-containing DASY molecular sieve, USY molecular sieve, rare earth-containing USY molecular sieve, REY molecular sieve, REHY molecular sieve, and HY molecular sieve.

The catalyst B used in the present invention may be any catalyst suitable for catalytic cracking of light feedstocks.

According to some specific embodiments of the present invention, wherein, the B catalyst comprises the following components by weight percentage: 15-40% of natural minerals, 50-75% of ZSM-5 molecular sieve or modified ZSM-5 molecular sieve, 10- 35% Y-type molecular sieve.

The natural mineral is selected from at least one of kaolin, halloysite, montmorillonite, diatomite, attapulgite, sepiolite, halloysite, hydrotalcite, bentonite, and rectorite. The Y-type molecular sieve is selected from at least one of DASY molecular sieve, rare earth-containing DASY molecular sieve, USY molecular sieve, rare earth-containing USY molecular sieve, REY molecular sieve, REHY molecular sieve, and HY molecular sieve.

According to some specific embodiments of the present invention, wherein, the particle size distribution of catalyst B: particles with a particle size of 30-50 μm account for 80-100 wt % of the total weight of catalyst B.

According to some specific embodiments of the present invention, wherein, the method further comprises regenerating the deactivated catalyst after the reaction, and separating and enriching the regenerated catalyst twice to obtain regenerated A catalyst rich in A catalyst, and Regenerate B catalyst rich in B catalyst, then regenerated A catalyst is transported for heavy feedstock catalytic cracking reaction, and regenerated B catalyst is transported for light feedstock catalytic cracking reaction.

According to some specific embodiments of the present invention, wherein, the weight ratio of the A catalyst and the B catalyst in the regenerated A catalyst delivered for the catalytic cracking reaction of heavy feedstock oil is 7:3 to 9:1; The weight ratio of the B catalyst to the A catalyst in the regenerated B catalyst for the oil catalytic cracking reaction is 7:3 to 9:1.

According to some specific embodiments of the present invention, wherein, the weight ratio of the A catalyst and the B catalyst in the regenerated A catalyst sent for the catalytic cracking reaction of the heavy feedstock oil is 8:2.

According to some specific embodiments of the present invention, wherein, the weight ratio of the B catalyst and the A catalyst in the regenerated B catalyst sent for the light feedstock catalytic cracking reaction is 8:2.

According to some specific embodiments of the present invention, wherein, in the petroleum hydrocarbon catalytic cracking reaction system, the weight ratio of the A catalyst and the B catalyst is 6:4 to 9:1.

According to some specific embodiments of the present invention, wherein, in the petroleum hydrocarbon catalytic cracking reaction system, the weight ratio of the A catalyst and the B catalyst is 7:3 to 8:2.

According to some specific embodiments of the present invention, wherein, the light feedstock oil comprises a mixture of one or more of hydrocarbon fractions, gasoline fractions, and diesel fractions rich in one or more of C4, C5, and C6 ; The heavy feedstock oil includes one or more mixtures of petroleum hydrocarbons, oil sand bitumen, mineral oil, synthetic oil, animal fat, and vegetable fat.

The gasoline and diesel fractions can be part of the gasoline and diesel fractions obtained from the reaction, or one or more mixtures of catalytic cracking, thermal cracking, coking gas, diesel fractions, straight-run gasoline, and diesel fractions.

The invention realizes the hydrocarbons conversion by partitioning the catalyst, enriches the mixed catalysts of different properties and transports them to different reaction zones, and matches different raw materials at the same time, improves the matching degree between the catalyst and the raw materials, and makes up for the inability of the same catalyst to take into account many factors. Due to the defects of raw materials of this nature, the efficiency of the catalyst is greatly improved, and at the same time, the conversion of hydrocarbons (such as cracking, aromatization, isomerization, superposition and other reactions) can be directionally controlled, and the selectivity of the target product can be improved. In addition, by adjusting the process parameters, the occurrence of side reactions can be greatly reduced. For example, in the reaction of the main reactor, the reaction temperature is lowered to moderately crack the heavy raw materials, and the reaction temperature is increased in the secondary reactor to make the light raw materials fully react, so as to reduce the yield of dry gas and coke.

According to some specific embodiments of the present invention, the reaction conditions for the catalytic cracking reaction of the heavy feedstock oil include: the preheating temperature of the heavy feedstock oil is 160-350°C, the reaction temperature is 460-550°C, and the agent-oil ratio is 4-12 , the micro-reaction activity of the catalyst is 50-70, the reaction time is 1.0-7.0s, and the reaction pressure is 0.1-0.4MPa; the reaction conditions for the catalytic cracking reaction of the light feedstock oil include: the preheating temperature of the light feedstock oil is 40-200°C, the reaction The temperature is 460-600°C, the agent-oil ratio is 4-15, the catalyst micro-reaction activity is 50-80, the reaction time is 0.3-7s, and the reaction pressure is 0.1-0.4MPa.

According to some specific embodiments of the present invention, the reaction conditions for the catalytic cracking reaction of the heavy feedstock oil include: the preheating temperature of the heavy feedstock oil is 180-280°C.

According to some specific embodiments of the present invention, the reaction conditions for the catalytic cracking reaction of the heavy feedstock oil include: the reaction temperature is 490-530°C.

According to some specific embodiments of the present invention, the reaction conditions for the catalytic cracking reaction of heavy feedstock oil include: the ratio of agent to oil is 6-9.

According to some specific embodiments of the present invention, the reaction conditions for the catalytic cracking reaction of heavy feedstock oil include: catalyst micro-reactivity 58-65.

According to some specific embodiments of the present invention, the reaction conditions for the catalytic cracking reaction of the heavy feedstock oil include: a reaction time of 1.5-4.5s.

According to some specific embodiments of the present invention, the reaction conditions for the catalytic cracking reaction of the light feedstock oil include: the preheating temperature of the light feedstock oil is 60-150°C.

According to some specific embodiments of the present invention, the reaction conditions of the light feedstock catalytic cracking reaction include: the reaction temperature is 500-580°C.

According to some specific embodiments of the present invention, the reaction conditions for the catalytic cracking reaction of light feedstock oil include: the ratio of agent to oil is 6-9.

According to some specific embodiments of the present invention, the reaction conditions of the light feedstock catalytic cracking reaction include: catalyst micro-reactivity of 60-75.

According to some specific embodiments of the present invention, the reaction conditions for the catalytic cracking reaction of the light feedstock oil include: a reaction time of 1-6 s.

According to some specific embodiments of the present invention, wherein the method comprises performing a catalytic cracking reaction using the apparatus described in any of the preceding aspects of the present invention.

According to some specific embodiments of the present invention, wherein, the primary cyclone separator of catalyst A has an inlet gas velocity of 6-12 m/s; the primary cyclone separator of catalyst B has an inlet gas velocity of 12-22 m/s, and the primary cyclone of catalyst B has a limited inlet gas velocity of 12 to 22 m/s. The gas velocity at the inlet of the separator is 6-10 m/s higher than that at the inlet of the primary separation separator of A catalyst.

According to some specific embodiments of the present invention, wherein, the method comprises drawing the regenerated catalyst mixture (mixture of A catalyst and B catalyst) from the regenerator through a first regeneration inclined pipe, passing through a regeneration catalyst standpipe, and then passing through A catalyst The primary cyclone separator separates and enriches the heavy catalyst A with larger particles, and sends it back to the regenerator through the A catalyst conveying pipe, and the regenerated A catalyst rich in A catalyst is conveyed to the bottom end of the main reactor through the third regeneration inclined pipe It reacts with heavy raw materials; the unseparated catalyst mixture rich in B catalyst is separated and enriched with B catalyst with smaller particles through the B catalyst initial cyclone separator to obtain a regenerated B catalyst rich in B catalyst, and in the B catalyst After being collected in the storage tank, it is transported to the bottom of the sub-reactor through the second regeneration inclined pipe to react with the light raw materials.

According to some specific embodiments of the present invention, the overflow gas enters the top of the regenerator and is separated by a cyclone separator and then discharged together with the flue gas.

To sum up, the present invention provides a catalyst zone catalytic cracking method and device. The method of the present invention has the following advantages:

The technological advantage of the present invention lies in that two kinds of catalysts are used directionally and matched according to the properties of the raw materials and the production purpose. After regeneration, the catalysts A and B are respectively enriched and transported to different reactors to contact and react with the raw materials of different properties. The partitioning of the catalyst and the partitioned feed enable a high degree of directional matching of the catalyst and the feed. And according to the characteristics of the catalytic reaction in different zones, the optimized process conditions are matched to achieve a high degree of matching of catalysts, raw materials and process conditions, so as to improve the directional conversion efficiency of raw materials and the directional catalytic efficiency of catalysts, thereby strengthening the catalytic cracking capacity. The catalytic performance of the catalyst enables the catalytic performance of the catalyst to be fully exerted. When the catalysts are mixed and used, the influence of one catalyst on another catalyst is avoided, the generation of by-products is reduced, and the yield of the target product is improved.

Description of drawings

FIG. 1 is a schematic diagram of the apparatus of Embodiment 1 of the present invention.

Detailed ways

The implementation process and beneficial effects of the present invention are described in detail below through specific examples, which are intended to help readers better understand the essence and characteristics of the present invention, and are not intended to limit the scope of implementation of the present case.

The device connection relationship of each embodiment is shown in FIG. 1 .

The method is to connect the first regeneration inclined pipe 16 to the regenerated catalyst standpipe 18 outside the regenerator 14 of the conventional double riser catalytic cracking device, and the regenerated catalyst standpipe 18 is connected to the A catalyst initial cyclone separator 19, and the A catalyst initial swirl separator 19 is connected. The lower end of the cyclone separator 19 is connected with the regenerator 14 by the A catalyst conveying pipe 21, and the upper end of the A catalyst primary cyclone separator 19 is connected with the B catalyst primary cyclone separator 20, and the B catalyst primary cyclone separator 20 is in the B catalyst storage tank 22. Inside, the upper part of the B catalyst primary spin separator 20 is connected to the upper part of the regenerator 14 , and the lower part of the B catalyst storage tank 22 is connected to the secondary reactor 11 by the second regeneration inclined pipe 24 .

The process is that the preheated heavy feedstock oil 1 enters from the lower part of the main reactor 3, and reacts with the regenerated A catalyst rich in A catalyst from the regenerator 14 under the lifting action of the pre-lifting steam 2, while rising, The reacted oil and gas and A catalyst are separated into oil and gas under the action of the primary cyclone separator 6, the oil and gas continue to rise, and the oil and gas 8 is obtained after passing through the secondary cyclone 7, and the oil and gas 8 enters the cooling separation system for cooling and separation. After being stripped by the stripping steam 9 in the stripping section 4, the swirled catalyst is transported to the regenerator 14 through the inclined pipe 13 to be regenerated for regeneration.

The preheated light feedstock oil 10 is introduced into the lower part of the sub-reactor 11, and reacts with the regenerated B-catalyst rich in the B-catalyst from the B-catalyst storage tank 22 in the sub-reactor 11. After the reaction, the oil and gas and the deactivated catalyst are initially Preliminary separation in the cyclone 12, and then separated by the secondary cyclone 7 to obtain oil and gas discharge, the deactivated catalyst enters the stripping section 4 through the settler 5, and is stripped by the stripping steam 9. 13 is sent to the regenerator 14 for regeneration.

The deactivated catalyst entering the regenerator 14 is regenerated under the action of the regeneration air 15. The regenerated regenerated catalyst is led out of the regenerator 14 through the first regeneration inclined pipe 16, and is lifted into the regenerator 14 under the action of the regenerated catalyst standpipe 18 and the lifting wind 17. A catalyst primary cyclone separator 19, A catalyst is enriched in the A catalyst primary cyclone separator 19, and the enriched regenerated A catalyst enters the regenerator 14 through the A catalyst transport pipe 21, and is then introduced into the third regeneration inclined pipe 25 To the bottom of the main reactor 3, it is contacted and reacted with the heavy feedstock oil. The catalyst that is not separated by the A catalyst primary cyclone separator 19 enters the B catalyst primary cyclone separator 20, so that the B catalyst is enriched to obtain a regenerated B catalyst rich in the B catalyst, and is stored in the B catalyst storage tank 22 for regeneration. Under the action of the loosening wind 23, the B catalyst is introduced into the bottom of the secondary reactor 11 through the second regeneration inclined pipe 24 to contact and react with the light feedstock oil, and the overflow gas 26 from the top of the B catalyst primary cyclone separator enters the regenerator.

The properties of the heavy feedstock oil are shown in Table 1. The light feedstock oil is the gasoline fraction and C4 hydrocarbons generated by the primary cracking of the heavy feedstock oil.

Table 1 Properties of heavy raw materials

project data project data Density(20℃)kg/m³ 914 Nitrogen content, wt% 0.02 Carbon residue, wt% 0.24 Hydrocarbon composition analysis Elemental analysis Saturated hydrocarbons, wt% 69.8 Hydrogen content, wt% 12.57 Aromatics, wt% 23.7 Carbon content, wt% 86.67 Gum, wt% 6.1 Sulfur content, wt% 0.33 Asphaltene, wt% <0.4

Example 1

The main reactor is a riser reactor, and the secondary reactor is a riser + bed reactor. The properties of catalysts A and B are shown in Table 2. The composition of the catalyst delivered to the main reactor is: 70wt%A+30wt%B, and the composition of the catalyst delivered to the secondary reactor: 70wt%B+30wt%A. The main process conditions are as follows

As shown in Table 3, the reaction results are shown in Table 4.

Table 2 Catalyst properties

Table 3 Main process conditions

Preheating temperature of heavy raw materials, °C 240 Preheating temperature of light raw materials, °C 100 Main reactor reaction temperature, °C 500 Side reactor reaction temperature, °C 540 The ratio of agent to oil in the main reactor 7 The ratio of agent to oil in the side reactor 6 Main reactor reaction time, s 7 Side reactor reaction time, s 4 Main reactor reaction pressure, MPa 0.3 Side reactor reaction pressure, MPa 0.3 Catalyst microreactivity A: 50B: 60 Regeneration temperature, °C 680

Table 4 Product distribution

Example 1 Comparative example (DCC-plus process) Product yield, wt% dry gas 6.24 7.54 liquefied gas 40.26 40.16 C5+ gasoline 33.21 30.17 diesel fuel 11.14 11.25 oil slurry 2.83 3.07 coke 5.76 7.23 Conversion rate, wt% 85.47 85.68 Total olefin yield, wt% 36.12 33.76 vinyl 4.55 3.86 acrylic 17.83 17.16 Butene 13.74 12.74

Example 2

The main reactor is a riser reactor, and the secondary reactor is a riser + bed reactor. The properties of catalysts A and B are shown in Table 5. The composition of the catalyst delivered to the main reactor is: 80wt%A+20wt%B, and the composition of the catalyst delivered to the secondary reactor: 80wt%B+20wt%A. The main process conditions are shown in Table 6 As shown, the reaction results are shown in Table 7.

Table 5 Catalyst properties

Table 6 Main process conditions

Preheating temperature of heavy feedstock oil, °C 240 Light stock oil preheating temperature, °C 100 Main reactor reaction temperature, °C 515 Side reactor reaction temperature, °C 560 The ratio of agent to oil in the main reactor 8 The ratio of agent to oil in the side reactor 7 Main reactor reaction time, s 8 Side reactor reaction time, s 5 Main reactor reaction pressure, MPa 0.3 Side reactor reaction pressure, MPa 0.3 Catalyst microreactivity A: 60B: 70 Regeneration temperature, °C 680

Table 7 Product distribution

Example 2 Comparative example (DCC-plus process) Product yield, wt% dry gas 5.44 7.54 liquefied gas 41.67 40.16 C5+ gasoline 34.18 30.17 diesel fuel 9.37 11.25 oil slurry 2.06 3.07 coke 6.41 7.23 Conversion rate, wt% 87.70 85.68 Total olefin yield, wt% 39.59 33.76 vinyl 5.88 3.86 acrylic 19.23 17.16 Butene 14.48 12.74

Example 3

The main reactor is a riser reactor, and the secondary reactor is a riser + bed reactor. The properties of the catalysts A and B are shown in Table 8. The composition of the catalyst delivered to the main reactor is: 90wt%A+10wt%B, and the composition of the catalyst delivered to the secondary reactor: 90wt%B+10wt%A. The main process conditions are shown in Table 9 As shown, the reaction results are shown in Table 10.

Table 8 Catalyst properties

Table 9 Main process conditions

Preheating temperature of heavy raw materials, °C 240 Preheating temperature of light raw materials, °C 100 Main reactor reaction temperature, °C 530 Side reactor reaction temperature, °C 580 The ratio of agent to oil in the main reactor 9 The ratio of agent to oil in the side reactor 8 Main reactor reaction time, s 9 Side reactor reaction time, s 6 Main reactor reaction pressure, MPa 0.3 Side reactor reaction pressure, MPa 0.3 Catalyst microreactivity A: 70B: 75 Regeneration temperature, °C 680

Table 10 Product distribution

Example 3 Comparative example (DCC-plus process) Product yield, wt% dry gas 5.24 7.54 liquefied gas 41.26 40.16 C5+ gasoline 34.46 30.17 diesel fuel 10.14 11.25 oil slurry 2.68 3.07 coke 5.37 7.23 Conversion rate, wt% 86.33 85.68 Total olefin yield, wt% 38.46 33.76 vinyl 5.49 3.86 acrylic 18.23 17.16 Butene 14.74 12.74

It can be seen from the data in the table that the yield of the target product is significantly improved by adopting the catalytic cracking process and device of the patented catalyst partition, for example, the yield of light olefins is increased by 2.36wt% to 5.83wt%, while the yield of by-products is significantly reduced , the yields of dry gas and coke are reduced by 1.30wt%-2.30wt% and 0.82wt%-1.86wt%, respectively.

Claims (18)

1. A catalyst subregional catalytic cracking device, wherein the device comprises a main reactor (3) for the catalytic cracking reaction of heavy stock oil, a secondary reactor (11) for the catalytic cracking reaction of light stock oil, The regenerator (14), the A catalyst preliminary cyclone separator (19) and the B catalyst storage tank (22), the B catalyst preliminary cyclone separator (20) is arranged above the interior of the B catalyst storage tank (22), and the regenerator (14) is respectively It is connected with the main reactor (3) and the A catalyst primary cyclone separator (19) through pipelines, the top of the A catalyst primary cyclone separator (19) is connected with the B catalyst primary cyclone separator (20) through pipelines, and the bottom is connected with the B catalyst primary cyclone separator (20). The pipeline is connected to the regenerator (14), the top of the B catalyst primary cyclone separator (20) is connected to the regenerator (14) through the pipeline, and the bottom of the B catalyst primary cyclone separator (20) is provided with the B catalyst storage tank (22) The opening communicated with the internal cavity, the bottom of the B catalyst storage tank (22) is connected to the secondary reactor (11) through a pipeline; the regenerator (14) is connected to the regenerated catalyst standpipe (18) through the first regeneration inclined pipe (16) ) bottom is connected, and the top of the regenerated catalyst standpipe (18) is connected with the A catalyst initial spin separator (19); the A catalyst initial spin separator (19) bottom is connected with the regenerator (14) through the A catalyst delivery pipe (21); The bottom of B catalyst storage tank (22) is connected with the secondary reactor (11) through the second regeneration inclined pipe (24); the regenerator (14) is connected with the main reactor (3) through the third regeneration inclined pipe (25). 2. The device according to claim 1, wherein the types of the main reactor (3) and the secondary reactor (11) are respectively independent riser reactor, transport bed reactor, riser+fast bed A combination of one or more of reactors, turbulent bed + fast bed reactors. 3. The device according to claim 1, wherein the A catalyst primary cyclone separator (19) is a cyclone separator capable of realizing A catalyst separation of 50-100 wt%, and its air inlet is opened at the upper or middle position; The B catalyst primary cyclone separator (20) is a cyclone separator capable of separating 50-100 wt% of the B catalyst, and its air inlet is opened at the upper or middle position. 4. The device according to claim 1, wherein the main reactor (3) and the secondary reactor (11) are respectively riser reactors; the top of the main reactor (3) and the bottom of the stripper (4) are respectively Connect and penetrate the stripper (4) into the settler (5), the top of the stripper (4) is connected with the bottom of the settler (5), and the top of the secondary reactor (11) is connected with the settler (5); the main reaction The bottom of the reactor (3) is connected with the regenerator (14) through the third regeneration inclined pipe (25); the bottom of the secondary reactor (11) is connected with the bottom of the B catalyst storage tank (22) through the second regeneration inclined pipe (24); The lower end of the lifter (4) is connected with the lower end of the regenerator (14) through the inclined pipe (13) to be grown. 5. The device according to claim 4, wherein, the first pre-cyclone separator (12) is provided in the settler (5), and the top of the secondary reactor (11) is connected with the first pre-cyclone separator (12) . 6. The device according to claim 5, wherein the second primary cyclone (6) connected with the main reactor (3) is also provided in the settler (5), and two pre-cyclones are provided at the top of the settler (5). A stage cyclone (7), the top of the second stage cyclone (7) communicates with the outside through the top of the settler (5). 7. The device according to claim 5, wherein a cyclone separator (27) is arranged in the upper part of the regenerator (14), and the top of the cyclone separator (27) communicates with the outside through a pipeline passing through the top of the regenerator (14). 8. A catalyst zoned catalytic cracking method, wherein the method comprises using the catalyst zoned catalytic cracking device according to any one of claims 1 to 7 to carry out a catalytic cracking reaction, comprising using two different catalysts in the petroleum hydrocarbon catalytic cracking reaction The catalyst includes catalyst A used in the catalytic cracking reaction of heavy feedstock oil, and catalyst B used in the catalytic cracking reaction of light feedstock oil; the bulk density of catalyst A is 0.8-1.5g/cm ³ ; the average particle size is 80-140 μm ; Particle size distribution: particles with a particle size larger than 80 μm account for 60-100 wt% of the total weight of catalyst A; B catalyst bulk density is 0.4-0.7 g/cm ³ ; Average particle size is 20-80 μm; Particle size distribution: 30-50 μm particles The diameter of the particles accounts for 60-100 wt% of the total weight of the catalyst B. 9. The method according to claim 8, wherein the bulk density of catalyst A is 0.9-1.2 g/cm ³ ; the average particle size is 90-120 μm; particle size distribution of catalyst A: particles with a particle size larger than 80 μm account for the total amount of catalyst A. The bulk density of catalyst B is 0.5-0.65 g/cm ³ ; the average particle size is 40-60 μm; particle size distribution: particles with a particle size of 30-50 μm account for 80-100 wt % of the total weight of catalyst B. 10. The method according to claim 8, wherein the method further comprises regenerating the deactivated catalyst after the reaction, and separating and enriching the regenerated catalyst twice to obtain regenerated A rich in A catalyst respectively. catalyst, and the regenerated B catalyst rich in the B catalyst, and then the regenerated A catalyst is transported for the heavy feedstock catalytic cracking reaction, and the regenerated B catalyst is transported for the light feedstock catalytic cracking reaction. 11. The method according to claim 10, wherein the weight ratio of the A catalyst and the B catalyst in the regenerated A catalyst conveyed for the catalytic cracking reaction of heavy feedstock is 7:3 to 9:1; The weight ratio of the B catalyst to the A catalyst in the regenerated B catalyst for the catalytic cracking reaction of the light feed oil is 7:3 to 9:1. 12. The method according to claim 11, wherein the weight ratio of A catalyst and B catalyst in the regenerated A catalyst conveyed for the catalytic cracking reaction of heavy stock oil is 8:2; The weight ratio of B catalyst and A catalyst in the regenerated B catalyst of the catalytic cracking reaction is 8:2. 13. The method according to any one of claims 8 to 12, wherein, in the petroleum hydrocarbon catalytic cracking reaction system, the weight ratio of catalyst A and catalyst B is 6:4 to 9:1. The method according to claim 13, wherein, in the petroleum hydrocarbon catalytic cracking reaction system, the weight ratio of the A catalyst and the B catalyst is 7:3 to 8:2. 15. The method according to any one of claims 8 to 12, wherein the light feedstock oil comprises hydrocarbon fractions, gasoline fractions, and diesel fractions rich in one or more of C4, C5, and C6 The heavy feedstock oil includes a mixture of one or more of petroleum hydrocarbons, oil sand bitumen, mineral oil, synthetic oil, animal fat, and vegetable fat. 16. The method according to any one of claims 8 to 12, wherein the reaction conditions for the catalytic cracking reaction of the heavy feedstock oil comprise: the preheating temperature of the heavy feedstock oil is 160-350°C; the reaction temperature is 460-550°C ; the ratio of agent to oil is 4-12; the micro-reactive activity of the catalyst is 50-70; the reaction time is 1.0-7.0s; the reaction pressure is 0.1-0.4MPa; The temperature is 40-200°C; the reaction temperature is 460-600°C; the agent-oil ratio is 4-15; the catalyst micro-reactivity is 50-80; the reaction time is 0.3-7s; and the reaction pressure is 0.1-0.4MPa. 17. The method according to claim 16, wherein the reaction conditions for the catalytic cracking reaction of the heavy feedstock oil comprise: the preheating temperature of the heavy feedstock oil is 180-280°C; the reaction temperature is 490-530°C; 6-9; catalyst micro-reactive activity 58-65; reaction time 1.5-4.5s; reaction conditions for the catalytic cracking reaction of light feedstock oil include: the preheating temperature of light feedstock oil is 60-150°C; the reaction temperature is 500-580°C ℃; the agent-oil ratio is 6-9; the catalyst micro-reactive activity is 60-75; the reaction time is 1-6s. 18. The method according to any one of claims 8 to 12, wherein the A catalyst primary cyclone separator defines an inlet gas velocity of 6-12 m/s; the B catalyst primary cyclone separator defines an inlet gas velocity of 12 to 12 m/s. 22m/s, the gas velocity at the inlet of the primary cyclone separator of the B catalyst is 6-10 m/s higher than the inlet gas velocity of the primary separation separator of the A catalyst.

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