CN102796556B - A kind of catalysis conversion method of petroleum hydrocarbon - Google Patents

Abstract

A kind of catalysis conversion method of petroleum hydrocarbon, high-sulfur wax oil and hot regenerated catalyst catalytic cracking unit reactor lower contacts and there is cracking reaction, the oil gas generated and under certain reaction environment, optionally hydrogen transfer reactions and isomerization reaction occur containing the catalyzer of charcoal is up, separating reaction oil gas obtains comprising liquefied gas, the reaction product of gasoline and catalytic wax oil, reclaimable catalyst is through stripping, regeneration Posterior circle uses, wherein catalytic wax oil and other optional secondary processing wax oil enter aromatics seperation unit and carry out aromatics seperation, preferred gained is rich in non-aromatics cut and turns back to catalytic cracking unit.The method improves liquid yield and productivity of propylene, provides a new approach for oil refining production process cleans to clean with refined oil product.

Description

A kind of catalytic conversion method of petroleum hydrocarbon

technical field

The invention belongs to a catalytic conversion method of petroleum hydrocarbons, more specifically, relates to a catalytic conversion method of an integrated process of catalytic cracking of inferior wax oil and separation of aromatic hydrocarbons.

Background technique

The processing of high-sulfur and low-quality wax oil raw materials by conventional catalytic cracking technology not only makes the SO _X emission in the catalytic cracking regeneration flue gas not meet the environmental protection requirements, but also the sulfur content in gasoline and diesel products cannot meet the product specification requirements. Therefore, usually these high-sulfur low-quality wax oil raw materials are first hydrotreated to remove impurities such as sulfur, nitrogen and metals, saturate the polycyclic aromatic hydrocarbons in the raw materials, and improve their catalytic cracking reaction performance, and then use them as raw materials for catalytic cracking to produce low Sulfur gasoline and diesel.

US4780193 discloses a method for improving the quality of catalytic cracking raw materials by using hydrorefining technology. The reaction temperature of the hydrorefining unit is lower than 390° C., and the reaction pressure is at least 10.0 MPa, preferably 12.0 MPa. Under the process conditions that are favorable for the saturation of aromatics, the cracking performance of the raw material of the catalytic cracking unit is improved by hydrofining, thereby increasing the conversion rate of the catalytic cracking unit and producing high-octane gasoline blending components. CN101684417A discloses an optimized hydrogenation-catalytic cracking combined process method. The wax oil raw material is reacted in the hydrotreating reaction zone, and the hydrogenated wax oil obtained is used as the catalytic cracking raw material oil, and directly enters the catalytic cracking unit without fractionation, and the catalyzed The heavy cycle oil is recycled back to the hydrotreating reaction zone, the gaseous phase flow at the top of the hot high-pressure separator and the catalytic light cycle and the optional gas oil enter the hydrotreating reaction zone for hydrogenation and upgrading reaction, and the reaction product is fractionated to obtain Hydrogenated Naphtha and Hydrogenated Diesel. The hydrogen treatment unit and the hydrogenation upgrading unit share the hydrogen system, which reduces equipment investment and operating costs. The product scheme is flexible, and it can produce high-quality low-sulfur gasoline, high-quality diesel oil and reforming raw materials at the same time.

Generally, the catalytic cracking performance of low-quality wax oil raw materials can be improved after hydrotreating, but in the process of hydrotreating, some diesel oil, naphtha and light hydrocarbons will be produced due to the lighter distillation range, which is not conducive to the production of gasoline and propylene . In addition, the catalytic cracking process (MIP) that produces more isoparaffins treats high-quality catalytic cracking feedstock oil, especially hydrogenated wax oil, resulting in low olefin content in gasoline, low isobutene content in liquefied gas, and insufficient product distribution. , oil resources are not fully utilized.

The MIP process has been widely used, and has been applied to nearly 50 sets of catalytic cracking units, and has achieved huge economic and social benefits. See ZL99105904.2, ZL99105905.0 and ZL99105903.4 for a detailed description of the MIP technology of liquefied gas rich in isobutane and gasoline rich in isoparaffins.

Hydroprocessing often requires a large investment. The aromatics extraction treatment process has the advantages of small investment and quick return. It can not only achieve good results in heavy oil treatment, but also produce aromatics, an important chemical raw material by-product. For this reason, patent CN100350020C discloses a kind of catalytic cracking processing technology of low-quality oil. In this method, the light diesel oil fraction obtained by catalytic cracking of low-quality oil is returned to the catalytic cracking unit for re-refining, and the obtained heavy oil fraction is subjected to solvent extraction, and the extracted heavy aromatics As a product, raffinate is returned to the catalytic cracking unit for refining. This method solves the problem of heavy oil to a certain extent, but this method needs to control the final boiling point of the light diesel oil fraction to be ≤300°C and the heavy diesel oil fraction to be ≤450°C, wherein the light diesel oil fraction is returned to the catalytic cracking unit for re-refining, and the heavy diesel oil Enter the aromatics extraction unit for extraction, and the raffinate oil returns to the catalytic cracking unit. As a result, although the amount of oil slurry has decreased, it is still relatively high, and there is no diesel product, and the dry gas output is also large. Patent CN1766059A discloses a method for processing inferior heavy oil or residual oil. In this method, firstly, the raw material of heavy oil or residual oil enters a solvent extraction device, and the excess deasphalted oil enters a fixed-bed hydrotreating device for hydrogenation. The hydrogen tail oil enters the catalytic cracking unit, where part or all of the obtained oil slurry enters the magnetic floating bed hydrogenation unit together with the deasphalted oil obtained by solvent extraction, and the product is separated to obtain light fractions and unconverted tail oil, of which the unconverted tail oil The oil is recycled to the solvent extraction unit. The method organically combines the catalytic cracking process, the extraction process and the hydrogenation process, and has a certain effect on heavy oil treatment, but the process distillation range of the method is complex and the liquid yield is low.

With the increasingly stringent environmental protection regulations on the production process and product quality of catalytic cracking, even if the catalytic cracking process is used to treat hydrogenated wax oil, the SO _x emissions in the catalytic cracking regeneration flue gas cannot meet the environmental protection requirements, and it is still necessary to increase the regeneration flue gas treatment device. When the regenerative flue gas treatment device treats flue gas with lower content of SO _x , its treatment efficiency will be reduced. In addition, even though hydrogenated wax oil catalytic cracking produces gasoline with low sulfur content, it is still difficult to reduce the sulfur content in gasoline to below 10 μg/g, and gasoline still needs after-treatment. When S-Zorb technology is used to treat gasoline with low sulfur content, it is difficult to maintain the balanced operation of S-Zorb because the sulfur content in gasoline is too low, and it is necessary to supplement other sulfur compounds from the outside, resulting in a decrease in the use efficiency of the S-Zorb unit .

Contents of the invention

The purpose of the present invention is to provide a catalytic conversion method of an integrated process of catalytic cracking of inferior wax oil and separation of aromatics. First kind of embodiment of the present invention is as follows:

Catalytic conversion method provided by the invention comprises the following steps:

(1) The high-sulfur wax oil contacts with the thermally regenerated catalyst in the lower part of the catalytic cracking unit reactor and undergoes cracking reaction, and the generated oil gas and carbon-containing catalyst go up in a certain reaction environment to undergo selective hydrogen transfer reaction and isomerization Chemical reaction, separation and reaction of oil and gas to obtain reaction products including liquefied petroleum gas, gasoline, diesel oil and catalytic wax oil, and the raw catalyst is recycled after being stripped and regenerated;

(2) Catalyzed wax oil from step (1) and optional other secondary processed wax oil are used as raw material oil of the aromatics separation unit, and enter the aromatics separation unit for aromatics separation to obtain aromatics-rich fractions and non-aromatics-rich fractions.

The fraction rich in non-aromatics obtained in step (2) is returned to the catalytic cracking unit of step (1) or other catalytic cracking devices as feed oil for catalytic cracking.

The gasoline of step (1) enters the gasoline desulfurization device, and the diesel oil enters the diesel oil desulfurization device;

The regenerated flue gas in step (1) enters the flue gas treatment device for treatment, and the treated flue gas is discharged.

Catalytic conversion method provided by the invention is implemented like this:

(1), catalytic cracking unit

(a) The preheated high-sulfur low-quality raw material oil enters the reactor and contacts with the hot regenerated catalyst and undergoes cracking reaction. The reaction temperature is 490°C-620°C, preferably 500°C-600°C, and the reaction time is 0.5 seconds to 2.0 seconds, preferably 0.8 seconds to 1.5 seconds, the weight ratio of the catalyst to the raw oil (hereinafter referred to as the agent-oil ratio) is 3 to 15:1, preferably 3 to 12:1;

(b) The generated oil and gas and the used catalyst go up, and selective hydrogen transfer reaction and isomerization reaction occur in a certain reaction environment, and the reaction temperature is 420°C-550°C, preferably 460°C-500°C , the reaction time is 2 seconds to 30 seconds, preferably 3 seconds to 15 seconds, the weight ratio of the catalyst to the raw oil is 3 to 18:1, preferably 3 to 15:1, the water in the cracking reaction and hydrogen transfer reaction The weight ratio of steam to raw oil (hereinafter referred to as water-oil ratio) is 0.03-0.3:1, preferably 0.05-0.3:1, and the pressure is 130kPa-450kPa;

(c) Separating the reaction products to obtain propylene-rich liquefied gas, gasoline, diesel oil, catalytic wax oil and other products. The raw catalyst is stripped and sent to the regenerator, and recycled after burning.

(d) The catalytic wax oil enters the aromatics separation device directly or/and after removing a small amount of catalyst particles. Catalytic wax oil can remove a small amount of catalyst particles through filtering device or/and distillation device.

The reactor suitable for this method can be selected from one of equal-diameter riser, equal-linear-velocity riser, fluidized bed or variable-diameter riser, or a composite reactor composed of equal-diameter riser and fluidized bed. .

The method provided by the invention can be carried out in equal-diameter risers, equal-linear-velocity risers or fluidized-bed reactors, wherein the medium-diameter risers are the same as the conventional catalytic cracking reactors in refineries, and the flow rate of fluid in the equal-linear-velocity risers Line speed is basically the same. Equal-diameter riser and constant-linear-velocity riser reactors are pre-lift section, first reaction zone, and second reaction zone from bottom to top; fluidized bed reactors are first reaction zone and second reaction zone from bottom to top , The height ratio of the first reaction zone and the second reaction zone is 10-40:90-60. When using a riser of equal diameter, a riser of constant linear velocity or a fluidized bed reactor, one or more cooling medium inlets are provided at the bottom of the second reaction zone, and/or a heat extractor is arranged in the second reaction zone, The height of the heat extractor accounts for 50%-90% of the height of the second reaction zone. The temperature and reaction time of each reaction zone are controlled separately. The chilling agent is one or a mixture of more than one selected from chilling agent, cooled regenerated catalyst and cooled semi-regenerated catalyst. Wherein the cold shock agent is selected from liquefied gas, crude gasoline, stable gasoline, diesel oil, heavy diesel oil or a mixture of more than one in any proportion in water; the cooled regenerated catalyst and the cooled semi-regenerated catalyst are the catalysts to be regenerated respectively After two-stage regeneration and one-stage regeneration and cooling, the carbon content of the regenerated catalyst is less than 0.1% by weight, preferably less than 0.05% by weight, and the carbon content of the semi-regenerated catalyst is 0.1% to 0.9% by weight, preferably 0.15% by weight. % by weight to 0.7% by weight.

The method provided by the present invention can also be carried out in the compound reactor that is made of equal-diameter riser and fluidized bed, the equal-diameter riser of the bottom is the first reaction zone, and the fluidized bed of the top is the second reaction zone, respectively controlled The temperature and reaction time of each reaction zone. One or more cooling shock medium inlets are arranged at the bottom of the fluidized bed, and/or a heat collector is arranged in the second reaction zone, and the height of the heat collector accounts for 50% to 90% of the height of the second reaction zone. The temperature and reaction time of each reaction zone are controlled separately. The chilling agent is one or a mixture of more than one selected from chilling agent, cooled regenerated catalyst and cooled semi-regenerated catalyst. Wherein the cold shock agent is selected from liquefied gas, crude gasoline, stable gasoline, diesel oil, heavy diesel oil or a mixture of more than one in any proportion in water; the cooled regenerated catalyst and the cooled semi-regenerated catalyst are the catalysts to be regenerated respectively After two-stage regeneration and one-stage regeneration and cooling, the carbon content of the regenerated catalyst is less than 0.1% by weight, preferably less than 0.05% by weight, and the carbon content of the semi-regenerated catalyst is 0.1% to 0.9% by weight, preferably 0.15% by weight. % by weight to 0.7% by weight.

The method provided by the present invention can also be carried out in a novel variable-diameter riser reactor, see ZL99105903.4 for detailed description. The diameter of the pre-lift section is the same as that of a conventional equal-diameter riser reactor, generally 0.02 to 5 meters, and its height accounts for 5% to 10% of the total height of the reactor. The role of the pre-lift section is to move and accelerate the regenerated catalyst upwards in the presence of a pre-lift medium, the same as that used in conventional equal-diameter riser reactors, selected from steam or dry gas.

The structure of the first reaction zone is similar to a conventional equal-diameter riser reactor, and its diameter can be the same as that of the pre-lift section, or slightly larger than that of the pre-lift section. The ratio of the diameter of the first reaction zone to the diameter of the pre-lift section is 1.0～2.0:1, its height accounts for 10%～30% of the total height of the reactor. After the feedstock oil and catalyst are mixed in this zone, the cracking reaction mainly occurs at a relatively high reaction temperature, catalyst-to-oil ratio, and short residence time (generally 0.5 seconds to 2.5 seconds).

The second reaction zone is thicker than the first reaction zone, the ratio of its diameter to the diameter of the first reaction zone is 1.5-5.0:1, and its height accounts for 30%-60% of the total height of the reactor. Its function is to reduce the flow rate and reaction temperature of oil gas and catalyst. The method for reducing the reaction temperature in this zone can be to inject a cooling shock medium from the junction of this zone and the first reaction zone, and/or by setting a heat collector in this zone to take away part of the heat to reduce the reaction temperature in this zone, so as to achieve The purpose of inhibiting secondary cracking reaction, increasing isomerization reaction and hydrogen transfer reaction. The chilling medium is one or a mixture of more than one selected from chilling agents, cooled regenerated catalysts and cooled semi-regenerated catalysts in any proportion. Wherein the cold shock agent is selected from liquefied gas, crude gasoline, stable gasoline, diesel oil, heavy diesel oil or a mixture of more than one in any proportion in water; the cooled regenerated catalyst and the cooled semi-regenerated catalyst are the catalysts to be regenerated respectively After two-stage regeneration and one-stage regeneration and cooling, the carbon content of the regenerated catalyst is less than 0.1% by weight, preferably less than 0.05% by weight, and the carbon content of the semi-regenerated catalyst is 0.1% to 0.9% by weight, preferably 0.15% by weight. % by weight to 0.7% by weight. If a heat extractor is provided, its height accounts for 50% to 90% of the height of the second reaction zone. The residence time of the stream in the reaction zone can be longer, ranging from 2 seconds to 30 seconds.

The structure of the outlet zone is similar to the top outlet part of a conventional equal-diameter riser reactor, the ratio of its diameter to the diameter of the first reaction zone is 0.8-1.5:1, and its height accounts for 0-20% of the total height of the reactor. The stream can stay in this zone for a certain period of time to suppress the overcracking reaction and thermal cracking reaction and increase the fluid flow rate.

The high-sulfur wax oil suitable for this method is selected from atmospheric tower top oil, distillate oil extracted from atmospheric tower, straight-run vacuum gas oil, lightly hydrogenated wax oil, coking gas oil (CGO), deasphalted oil (DAO ) and mixtures thereof, characterized in that the sulfur content should be greater than 0.5% by weight, preferably greater than 1.0% by weight.

The other secondary processing wax oils in step (2) are selected from CGO, DAO and mixtures thereof.

The two reaction zones in the method can be applied to all catalysts of the same type, which can be amorphous silica-alumina catalysts or zeolite catalysts. The active components of zeolite catalysts are selected from Y-type zeolite, HY-type zeolite, ultra-stable Y-type Type zeolite, ZSM-5 series zeolite or high silica zeolite with five-membered ring structure, ferrierite zeolite or a mixture of more than one in any proportion, the zeolite may contain rare earth and/or phosphorus, and may not contain rare earths and phosphorus.

The two reaction zones in the method may also be suitable for different types of catalysts, and the different types of catalysts may be catalysts with different particle sizes and/or catalysts with different apparent packing densities. Catalysts with different particle sizes and/or active components on catalysts with different apparent bulk densities are selected from different types of zeolites. A mixture of one or more than one of ferrierite and ferrierite with a membered ring structure in any proportion. The zeolite may contain rare earth and/or phosphorus, or may not contain rare earth and phosphorus. Catalysts with different particle sizes and/or high and low apparent bulk densities can enter different reaction zones, for example, catalysts with large particles containing ultrastable Y-type zeolite enter the first reaction zone to increase cracking reactions, and rare earth Y-type zeolite containing Small particles of zeolite catalysts enter the second reaction zone to increase the hydrogen transfer reaction. Catalysts with different particle sizes are stripped in the same stripper and regenerated in the same regenerator, and then the large and small particle catalysts are separated, and the small particle catalysts are cooled. into the second reaction zone. Catalysts with different particle sizes are separated by 30-40 microns, and catalysts with different apparent bulk densities are separated by 0.6-0.7 g/cm ³ .

(2) Aromatics separation unit

The aromatics separation unit process is a treatment process for separating the functions of aromatics and non-aromatics. The aromatics extraction/extraction process is preferred. Chemical methods or physical methods can be used. Physical methods are preferred. Single-solvent extraction can also be used. Using multi-solvent extraction.

The aromatics extraction/extraction process may include equipment such as an extraction tower, a stripping tower, and an extraction recovery tower.

The solvent is selected from one or a mixture of dimethylsulfoxide, furfural, dimethylformamide, monoethanolamine, ethylene glycol, 1,2-propanediol and the like. The solvent is recovered and recycled during the extraction process. The extraction temperature is 40-200° C., and the volume ratio between the solvent and the raw material is 0.4-6.0. The extract is heavy aromatics, one of the target products, and the raffinate, that is, non-aromatics, is used as one of the raw materials for hydrocarbon processing such as catalytic cracking.

The catalytic gas oil (FGO) is a fraction with an initial boiling point of not less than 260° C., and a hydrogen content of not less than 10.5% by weight. In a more preferred embodiment, the catalytic wax oil is a fraction with an initial boiling point of not less than 330° C., and a hydrogen content of not less than 10.8% by weight. The secondary processed wax oils are coker gas oil (CGO), deasphalted oil (DAO) and mixed raw oils thereof.

(3) Other auxiliary units

The gasoline from the catalytic cracking unit is sent to the gasoline hydrodesulfurization or gasoline adsorption desulfurization unit for gasoline desulfurization, respectively see patent CN101314734A or CN1658965A for details, the diesel oil from the catalytic cracking unit enters the diesel desulfurization unit for diesel desulfurization; the regenerated flue gas from the catalytic cracking unit enters the flue gas The gas treatment device is used for flue gas treatment, and the treated flue gas is discharged.

The advantages of the present invention are:

1. Improve the use efficiency of different refining technologies, strengthen the more reasonable integration of refining technologies, and provide a new way for cleaning the refining production process and refining products.

2. Since there is no hydrogenation pretreatment step for high-sulfur gas oil, the total hydrogen consumption of the refinery is reduced.

3. Increase the total liquid yield and butene yield, improve the selectivity of propylene, and produce aromatics by-product.

Description of drawings

Fig. 1 is a schematic flow chart of the principle of the catalytic cracking and aromatics extraction integrated process method provided by the present invention.

Figure 2 is a schematic flow diagram of a preferred embodiment of the present invention.

Detailed ways

The method provided by the present invention will be further described below in conjunction with the accompanying drawings, but the present invention is not limited thereto.

Fig. 1 is a schematic flow chart of the principle of the catalytic cracking and aromatics extraction integrated process method provided by the present invention.

The high-sulfur wax oil raw material enters the catalytic cracking reaction unit for catalytic cracking reaction, and the catalytic wax oil fraction separated from the catalytic cracking reaction unit is transported to the aromatics extraction unit for aromatics extraction to obtain aromatics-rich fractions and non-aromatics-rich fractions. This non-aromatic-rich fraction can be returned to the original catalytic cracking unit or sent to other reaction units.

Figure 2 is a schematic flow diagram of a preferred embodiment of the present invention. Figure 2 is a schematic diagram of the integrated process flow of catalytic cracking and aromatics extraction in a variable-diameter riser reactor. The shape and size of equipment and pipelines are not limited by the drawings, but determined according to specific conditions.

The numbers in Figure 2 are explained as follows:

1, 3, 4, 6, 11, 13, 17, 18, 21, 22, and 23 all represent pipelines; 2 is the pre-lift section of the riser; 5, 7 are the first reaction zone and the second reaction zone of the riser, respectively. 8 is the outlet area of the riser; 9 is the settler, 10 is the cyclone separator, 12 is the stripper, 14 is the inclined pipe to be produced, 15 is the regenerator, 16 is the regeneration inclined pipe, 19 is the separation system, 20 is an aromatics extraction device.

The pre-lift steam enters from the pre-lift section 2 of the riser through the pipeline 1, and the hot regenerated catalyst enters the pre-lift section of the riser through the regenerated inclined pipe 16 and is lifted by the pre-lift steam. The preheated raw oil enters from the pre-lifting section of the riser through the pipeline 4 and the atomized steam from the pipeline 3 in a certain proportion, mixes with the hot catalyst and enters the first reaction zone 5, and undergoes cracking reaction under certain conditions. The reactant stream is mixed with the chiller and/or cooled catalyzer (not shown among the figures) from the pipeline 6 and enters the second reaction zone 7 for secondary reaction. The reacted stream enters the outlet zone 8, and the reaction zone increases the flow rate. The linear velocity allows the reactant flow to quickly enter the settler 9 and the cyclone separator 10 in the gas-solid separation system, and the reaction product goes through the pipeline 11 to the separation system 19. After the reaction, the raw catalyst with charcoal enters the stripper 12, and after being stripped by the water vapor from the pipeline 13, it enters the regenerator 15 through the inclined pipe 14, and the raw catalyst is burnt and regenerated in the air from the pipeline 17. The gas exits the regenerator through the pipeline 18, and the hot regenerated catalyst returns to the bottom of the riser through the regenerating inclined pipe 16 for recycling.

In the separation system 19, dry gas, liquefied gas, gasoline, diesel oil (not shown) and catalytic wax oil are separated, wherein the catalytic wax oil is sent to the aromatics extraction unit 20 through the pipeline 21.

The catalytic wax oil and solvent (not shown in the figure) from the pipeline 21 enter the aromatics extraction device 20 for separation of aromatics and non-aromatics. The obtained fraction rich in aromatics is drawn out through line 23, and the fraction rich in non-aromatics is drawn out through line 22 and sent to To the catalytic cracking unit mixed with high sulfur gas oil for riser reactor or other catalytic cracking unit.

Example

The following examples will further illustrate the present invention, but do not limit the present invention thereby. The properties of the raw oil used in the examples and comparative examples are listed in Table 1. The trade mark of the catalytic cracking catalyst is CGP-1, and the commercial trade marks of the catalysts packed in the hydrotreating fixed-bed reaction zone in the comparative examples are RG-10A/RG respectively. -10B/RMS-1/RN-32V, the loading volume ratio is 4:4:15:77, the above catalysts are all produced by Sinopec Catalyst Branch, and the aromatics extraction solvent is furfural.

Example 1

This example illustrates the product distribution and product properties of raw material A after being treated by a medium-sized catalytic cracking unit and a medium-sized aromatics extraction unit using the method provided by the present invention.

The preheated raw material A is first processed in a medium-sized catalytic cracking unit. The total height of the pre-lifting section, the first reaction zone, the second reaction zone, and the outlet zone of the reactor of the medium-sized catalytic cracking unit is 15 meters, and the diameter of the pre-lifting section is 0.025 meters, its height is 1.5 meters; the diameter of the first reaction zone is 0.025 meters, its height is 4 meters; the diameter of the second reaction zone is 0.1 meters, its height is 6.5 meters; the diameter of the outlet zone is 0.025 meters, its height is 3 meters m; the vertex angle of the isosceles trapezoid in the longitudinal section of the joint of the first and second reaction zones is 45°; the base angle of the isosceles trapezoid in the longitudinal section of the joint of the second reaction zone and the outlet zone is 60°. The raw material A listed in Table 1 enters the reactor, and in the presence of water vapor, contacts and reacts with hot catalyst CGP-1, and separates the reaction products to obtain acid gas, dry gas, liquefied gas, catalytic gasoline, catalytic diesel, It can catalyze wax oil and coke and calculate its product distribution. The raw catalyst is stripped and enters the regenerator, and the regenerated catalyst is recycled after being burnt. Within a certain test time, a certain amount of catalytic wax oil is obtained to provide raw materials for the medium-sized aromatics extraction unit.

The catalytic wax oil is on the medium-sized aromatics extraction unit. The extraction section is 4.0 meters high and the inner diameter of the tower is 0.1 meters. The aromatics and non-aromatics in the catalytic wax oil are separated, and the non-aromatic-rich fraction provides raw materials for the medium-sized catalytic cracking unit. The operating conditions and catalysts of the medium-scale catalytic cracking unit for the non-aromatic-rich fraction are exactly the same as feedstock A. The total product distribution of the three tests is summed according to the specified ratio for the three sets of product distribution, and the properties of catalytic gasoline and catalytic diesel are mixed according to the specified ratio. Analyze the results. The test operating conditions, product distribution and product properties are listed in Tables 2 and 3.

Comparative example 1

Adopt medium-scale test device and catalyzer to be exactly the same as embodiment 1, the raw material oil used is also the raw material A listed in table 1. Only raw material A is hydrotreated in a medium-sized hydrotreating unit first, and the reaction product is separated to obtain acid gas, a small amount of dry gas, a small amount of liquefied gas, naphtha, hydrogenated diesel oil and hydrogenated catalytic wax oil. Within a certain test period, a certain amount of hydrogenated catalytic wax oil is obtained to provide raw materials for medium-sized catalytic cracking units. The operating conditions and catalysts for processing hydrogenated wax oil on a medium-sized catalytic cracking unit are completely the same as those of raw material A. The product distribution of the two sets of medium-sized test devices is summed according to the specified ratio, and the total product distribution of the two tests is obtained. The product distribution is listed in Table 2. The properties of catalytic gasoline, catalytic diesel and hydrogenated diesel are obtained through sample analysis. Its properties are listed in Table 3.

As can be seen from Tables 2 and 3, relative to the comparative example, the processing method of the present invention has no hydrogen consumption, and the total liquid yield (liquefied gas+gasoline+diesel oil+extracted oil) in the present invention is 91.87% by weight, compared with Comparative Example 1 Increased by 1.91 percentage points, the yield of isobutene rose from 1.31% by weight to 3.42% by weight, an increase of 161.07% by weight, the concentration of propylene rose from 30.71% by weight to 34.53% by weight, and the olefin content of gasoline rose from 12.3% by weight to 31.1% by weight.

Example 2

This example illustrates the product distribution and product properties of raw material B treated by a medium-sized catalytic cracking unit and a medium-sized aromatics extraction unit using the method provided by the present invention.

The preheated raw material B is first processed in a medium-sized catalytic cracking unit. The total height of the pre-lifting section, the first reaction zone, the second reaction zone, and the outlet zone of the reactor of the medium-sized catalytic cracking unit is 15 meters, and the diameter of the pre-lifting section is 0.025 meters, its height is 1.5 meters; the diameter of the first reaction zone is 0.025 meters, its height is 4 meters; the diameter of the second reaction zone is 0.1 meters, its height is 6.5 meters; the diameter of the outlet zone is 0.025 meters, its height is 3 meters m; the vertex angle of the isosceles trapezoid in the longitudinal section of the joint of the first and second reaction zones is 45°; the base angle of the isosceles trapezoid in the longitudinal section of the joint of the second reaction zone and the outlet zone is 60°. The raw material B listed in Table 1 enters the reactor, and in the presence of water vapor, contacts and reacts with the hot catalyst CGP-1, and separates the reaction products to obtain acid gas, dry gas, liquefied gas, catalytic gasoline, catalytic diesel, It can catalyze wax oil and coke and calculate its product distribution. The raw catalyst is stripped and enters the regenerator, and the regenerated catalyst is recycled after being burnt. Within a certain test time, a certain amount of catalytic wax oil is obtained to provide raw materials for the medium-sized aromatics extraction unit.

The catalytic wax oil is on the medium-sized aromatics extraction unit. The extraction section is 4.0 meters high and the inner diameter of the tower is 0.1 meters. The aromatics and non-aromatics in the catalytic wax oil are separated, and the non-aromatic-rich fraction provides raw materials for the medium-sized catalytic cracking unit. The non-aromatic-rich fraction is processed on the medium-sized catalytic cracking unit under the same operating conditions and catalysts as Feedstock B. The total product distribution of the three tests is summed according to the specified ratio for the three sets of product distribution, and the properties of catalytic gasoline and catalytic diesel are mixed according to the specified ratio. Analyze the results. The test operating conditions, product distribution and product properties are listed in Tables 2 and 3.

Comparative example 2

Adopt medium-scale test device and catalyzer to be exactly the same as embodiment 1, and the raw material oil used is also the raw material B listed in table 1. Only the raw material B is hydrotreated in a medium-sized hydrotreating unit first, and the reaction product is separated to obtain acid gas, a small amount of dry gas, a small amount of liquefied gas, naphtha, hydrogenated diesel oil and hydrogenated catalytic wax oil. Within a certain test period, a certain amount of hydrogenated catalytic wax oil is obtained to provide raw materials for medium-sized catalytic cracking units. The operating conditions and catalysts for the processing of hydrogenated wax oil in medium-sized catalytic cracking units are completely the same as those of raw material B. The product distribution of the two sets of medium-sized test devices is summed and calculated according to the specified ratio, and the total product distribution of the two tests is obtained. The product distribution is listed in Table 4. The properties of catalytic gasoline, catalytic diesel and hydrogenated diesel are obtained through sample analysis. Its properties are listed in Table 5.

As can be seen from Tables 4 and 5, compared with the comparative example, the present invention has no hydrogen consumption in processing, and the total liquid yield is 90.8% by weight, an increase of 3.71 percentage points, and the isobutylene yield is increased from 1.37% by weight to 2.92% by weight, an increase The concentration of propylene increased from 30.97% to 33.87% by weight, and the olefin content of gasoline increased from 16.6% to 33.1% by weight.

Table 1

Raw oil number A B Raw oil name High sulfur wax oil High sulfur wax oil Density (20℃), kg/ ^m3 907.7 933.7 Kinematic viscosity, ^mm2 /s 80℃ 11.53 10.67 100℃ 7.02 6.47 Carbon residue, wt% 0.30 0.67 Freezing point, ℃ 37 34 Nitrogen, weight % 0.12 0.21 Sulfur, wt% 1.80 3.26 Carbon, weight % 85.49 85.24 Hydrogen, weight % 12.34 11.53 Distillation range, ℃ initial boiling point 242 249 5% 349 342 10% 377 356 50% 446 427 70% 464 466 90% 498 530 end point 511 /

Table 2

Example 1 Comparative example 1 operating conditions catalytic unit Reaction temperature, ℃  First Reaction Zone/Second Reaction Zone 550/500 550/500 Dwell time, seconds 5.5 5.5  First Reaction Zone/Second Reaction Zone 2.0/3.5 2.0/3.5 Agent oil ratio 5.0 5.0 Water to oil ratio 0.1 0.1 Aromatics extraction unit temperature, ℃ 75 / Solvent Furfural / Catalytic wax oil/solvent ratio 2 / hydrogenation unit Hydrogen partial pressure, MPa / 8.0 Reaction temperature, ℃ / 370 Total volumetric space velocity, h ^-1 / 1.5 Hydrogen oil volume ratio, Nm ³ /m ³ / 500 Product distribution, weight % hydrogen sulfide 0.83 1.60 Ammonia / 0.12 dry gas 1.75 1.90 Liquefied gas 22.79 22.01 Of which propylene 7.87 6.76 Isobutylene 3.42 1.31 gasoline 45.12 39.74 Of which naphtha / 0.77 Catalytic gasoline 45.12 38.97 Light diesel oil 16.20 28.21 Of which hydrogenated diesel / 9.93 Catalytic diesel 16.20 18.28 extract oil (aromatics) 7.76 / heavy oil 0.60 1.77 Coke 4.95 5.75 Total 100.00 101.10 Total liquid yield, weight % 91.87 89.96 Chemical hydrogen consumption, wt% 0 1.10

table 3

Example 1 Comparative example 1 Properties and composition of catalytic gasoline octane number RON 93.8 93.6 MON 80.5 81.0 Distillation range, ℃ Initial boiling point to dry point 38～200 37～200 Sulfur content, μg/g 1140 100 Family composition, volume % Olefins 31.1 12.3 Aromatics 19.4 25.7 Catalytic Diesel Properties Density (20℃), kg/ ^m3 904.6 905.0 Sulfur content, weight % 2.3 0.20 Distillation range, ℃ 200～350 200～350 cetane number 29 28 Hydrogenated Diesel Properties Density (20℃), kg/ ^m3 / 856.4 Sulfur content, μg/g / 240 Distillation range, ℃ / 175～350

Table 4

Example 2 Comparative example 2 operating conditions catalytic unit Reaction temperature, ℃  First Reaction Zone/Second Reaction Zone 550/500 550/500 Dwell time, seconds 5.5 5.5  First Reaction Zone/Second Reaction Zone 2.0/3.5 2.0/3.5 Agent oil ratio 5.0 5.0 Water to oil ratio 0.1 0.1 Aromatics extraction unit temperature, ℃ 75 / Solvent Furfural / Catalytic wax oil/solvent ratio 2 / hydrogenation unit Hydrogen partial pressure, MPa / 10.0 Reaction temperature, ℃ / 370 Total volumetric space velocity, h ^-1 / 1.2 Hydrogen oil volume ratio, Nm ³ /m ³ / 550 Product distribution, weight % hydrogen sulfide 1.50 3.35 Ammonia / 0.21 dry gas 2.05 2.15 Liquefied gas 20.40 21.12 Of which propylene 6.91 6.54 Isobutylene 2.92 1.37 gasoline 42.62 39.27 Of which naphtha / 0.80 Catalytic gasoline 42.62 38.47 Light diesel oil 19.56 26.70 Of which hydrogenated diesel / 6.42 Catalytic diesel 19.56 20.28 extract oil (aromatics) 8.22 / heavy oil 0.59 2.22 coke 5.06 6.08 Total 100.00 101.10 Liquid yield, weight % 90.80 87.09 Chemical hydrogen consumption, wt% 0 1.10

table 5

Example 2 Comparative example 2 Properties and composition of catalytic gasoline octane number RON 94.8 94.5 MON 81.0 81.5 Distillation range, ℃ Initial boiling point to dry point 38～200 37～200 Sulfur content, μg/g 2080 200 Family composition, volume % Olefins 33.1 16.6 Aromatics 19.9 26.7 Catalytic Diesel Properties Density (20℃), kg/ ^m3 933.2 920.0 Sulfur content, weight % 3.6 0.60 Distillation range, ℃ 200～350 200～350 cetane number twenty three 26 Hydrogenated Diesel Properties Density (20℃), kg/ ^m3 / 868.7 Sulfur content, μg/g / 568 Distillation range, ℃ / 176～352

Claims (15)

1. a catalysis conversion method for petroleum hydrocarbon, is characterized in that the method comprises the following steps:

(1) high-sulfur wax oil and hot regenerated catalyst catalytic cracking unit reactor lower contacts and there is cracking reaction, the oil gas generated and under certain reaction environment, optionally hydrogen transfer reactions and isomerization reaction occur containing the catalyzer of charcoal is up, separating reaction oil gas obtains comprising liquefied gas, gasoline, the reaction product of diesel oil and catalytic wax oil, wherein gasoline enters gasoline sweetener, diesel oil enters diesel fuel desulfurization device, reclaimable catalyst is through stripping, regeneration Posterior circle uses, regenerated flue gas enters flue gas processing device and processes, fume emission after process,

(2) enter aromatics seperation unit from the catalytic wax oil of step (1) and other optional secondary processing wax oil and carry out aromatics seperation;

The sulphur content of described high-sulfur wax oil is greater than 0.5 heavy %.

2., according to the method for claim 1, it is characterized in that step (2) gained is rich in non-aromatics cut and turns back to catalytic cracking unit, as the stock oil of catalytic cracking.

3., according to the method for claim 1, it is characterized in that the sulphur content of described high-sulfur wax oil is greater than 1.0 heavy %.

4., according to the method for claim 1, it is characterized in that described high-sulfur wax oil is selected from atmospheric overhead, atmospheric tower is extracted out distillate, straight run decompressed wax oil, either shallow hydrogenation wax oil, wax tailings, deasphalted oil and composition thereof.

5., according to the method for claim 1, it is characterized in that other secondary processing wax oil described is selected from wax tailings, deasphalted oil and composition thereof.

6. according to the method for claim 1, it is characterized in that described cracking reaction condition is as follows: temperature of reaction is 490 DEG C ~ 620 DEG C, the reaction times is 0.5 second ~ 2.0 seconds, and the weight ratio of catalyzer and stock oil is 3 ~ 15: 1.

7. according to the method for claim 6, it is characterized in that described cracking reaction condition is as follows: temperature of reaction is 500 DEG C ~ 600 DEG C, the reaction times is 0.8 second ~ 1.5 seconds, and the weight ratio of catalyzer and stock oil is 3 ~ 12: 1.

8. according to the method for claim 1, it is characterized in that described hydrogen transfer reactions and isomerization reaction condition as follows: temperature of reaction is 420 DEG C ~ 550 DEG C, and the reaction times is 2 seconds ~ 30 seconds.

9. according to the method for claim 8, it is characterized in that described hydrogen transfer reactions and isomerization reaction condition as follows: temperature of reaction is 460 DEG C ~ 500 DEG C, and the reaction times is 3 seconds ~ 15 seconds.

10. according to the method for claim 1, it is characterized in that step (1) reactor used be selected from equal diameter riser tube, etc. one of in linear speed riser tube, fluidized-bed or reducing riser tube, or the compound reactor be made up of equal diameter riser tube and fluidized-bed.

11. according to the method for claim 10, and it is characterized in that reducing riser tube, the diameter ratio of second reaction zone and the first reaction zone is 1.5 ~ 5.0: 1.

12. according to the method for claim 1, it is characterized in that step (1) used be zeolite catalyst, its active ingredient is selected from y-type zeolite, ZSM-5 series zeolite or has the mixture of one or more the arbitrary proportion in the supersiliceous zeolite of five-membered ring structure, ferrierite.

13., according to the method for claim 12, is characterized in that described y-type zeolite is selected from HY type zeolite, ultrastable Y－type zeolite or its mixture.

14. according to the method for claim 1, it is characterized in that step (2) described aromatics seperation unit solvent for use is selected from one or more the mixture in methyl-sulphoxide, furfural, dimethyl formamide, monoethanolamine, ethylene glycol, 1,2-PD.

15., according to the method for claim 1, is characterized in that step (2) aromatics seperation condition is: extraction temperature is 40 ~ 200 DEG C, and the volume ratio between solvent and raw material is 0.4 ~ 6.0.