CN1333046C - Catalytic conversion process for petroleum hydrocarbons - Google Patents

Abstract

The present invention relates to a method for catalytic conversion of petroleum hydrocarbons, which comprises the following steps: (1) the petroleum hydrocarbons as raw materials are injected into a reaction zone A of a lift pipe to contact a regenerating agent in the reaction zone A and react with the regenerating agent, and a generated mixture of reaction oil gas and a catalyst flows upwards along the lift pipe to be supplied into a reaction zone C of a dense phase bed layer; (2) a separated C4 and/or C5 fraction coming from a product separating part is injected into a reaction zone B of the lift pipe to contact a regenerating agent in the reaction zone B and react with the regenerating agent, and a generated mixture of reaction oil gas and a catalyst flows upwards along the lift pipe to be supplied into the reaction zone C of the dense phase bed layer; (3) the mixture of the reaction oil gas and the catalyst, which comes from the reaction zone A of the lift pipe, and the mixture of the reaction oil gas and the catalyst, which comes from the reaction zone B of the lift pipe, converge in the reaction zone C of the dense phase bed layer and continue to react; (4) the reaction oil gas and the catalysts with deposited carbon after the reaction are separated, the reaction oil gas is conveyed into the product separating part, and the catalysts with the deposited carbon after the reaction is returned to a reaction part and circularly used after being stripped with steam and regenerated. The method can be used for increasing the ethene yield, the propene yield and the BTX yield.

Description

A kind of petroleum hydrocarbon catalytic conversion method

technical field

The invention relates to a method for catalytic conversion of petroleum hydrocarbons in the absence of hydrogen, more specifically, a method for catalytic conversion of petroleum hydrocarbons to increase the production of propylene and BTX.

Background technique

Light olefins have always been important synthetic monomers for petrochemical products and fuels. Now, light olefins are widely used in synthetic gasoline, polymers, antifreeze, petrochemical products, explosives, solvents, drugs, fumigants, resins, synthetic rubber and Many other products. Propylene is the second most important petrochemical synthetic monomer after ethylene.

At present, in the world, the main source of propylene needed for petrochemical synthesis is the by-product of ethylene plant tube furnace cracking, the output of propylene is about 15% by weight, accounting for 70% of market demand, petroleum refining (almost all comes from FCC) is the second largest source of propylene, accounting for the remaining 30% of market demand, while in the United States, almost 50% of propylene market demand comes from FCCU.

The main methods of producing low-carbon olefins from petroleum hydrocarbons are: tube furnace cracking with natural gas, naphtha or light diesel oil as raw materials, the main target product is low-carbon olefins; heat carrier cracking with heavy hydrocarbon raw materials ; And a catalytic conversion method using low-carbon alcohol as a raw material. Fluid catalytic cracking has been developed for more than 60 years and has been the main means of oil refining all over the world. It is the most efficient method of converting gas oil and residual oil into light oil. Catalytic cracking unit is the main process of secondary processing in my country's oil refining industry, which is used to produce liquefied gas, catalytic gasoline and diesel. Since the 1980s, the Academy of Petrochemical Sciences has successively developed a series of catalytic cracking family technologies, which have greatly changed the target products of catalytic cracking, mainly producing low-carbon olefins, or taking into account both oil and gas. Propylene is an important chemical raw material, and the diversity of its sources is also very important. Therefore, it is necessary to develop a catalytic conversion method that can greatly increase the production of propylene.

CN1218786A discloses a method for preparing ethylene and propylene by catalytic thermal cracking. It makes the preheated heavy petroleum hydrocarbon contact with the catalyst in the presence of water vapor in the riser or down-going conveyor line reactor, the reaction temperature is 650-750°C, the pressure is 150-400 kPa, and the reaction time is 0.2-5 seconds The catalytic pyrolysis reaction is carried out under the conditions that the agent-oil ratio is 15-40:1, and the weight ratio of water vapor and raw oil is 0.3-1:1. The process yields both ethylene and propylene in excess of 18% by weight. Thermal cracking dominates this reaction.

Disclosed in CN1102431A is a kind of catalytic conversion method for preparing low-carbon olefins, the reaction temperature is 480-680 ° C, the pressure is 120-400 kPa, the reaction time is 0.1-6 seconds, the agent-oil ratio is 4-20, water vapor and The weight ratio of raw oil is 0.01-0.5:1. The highest propylene yield was close to 20% by weight. A large amount of water vapor is injected during the reaction, and the catalytic reaction is dominant in this method.

USP5,846,403 discloses a method for catalytic naphtha re-cracking to produce light olefins with maximum yield. The method is carried out in a riser reactor containing two reaction zones, the lower part of the reactor is an upstream reaction zone, and the upper part is a downstream reaction zone. The raw material in the upstream reaction zone is light catalytic naphtha (boiling point below 140°C), the reaction conditions are: oil agent contact temperature 620°C-775°C, oil-gas residence time less than 1.5 seconds, agent-oil ratio 75-150, water vapor Accounting for 2-50% by weight of naphtha; the raw material in the downstream reaction zone is a conventional catalytic cracking raw material (boiling point is 220°C-575°C), the reaction conditions are: temperature 600°C-750°C, oil and gas residence time less than 20 seconds. Compared with conventional catalytic cracking, the oil and gas residence time in the upstream reaction zone of this method is too short, and the yield of liquefied gas is only increased by 0.97-1.21 percentage points.

WO00/40672 discloses a fluid catalytic cracking process with high olefin production. The method adopts the type of double-riser FCC device, injecting conventional FCC feedstock into one of the risers, contacting and reacting with the regenerated catalyst containing USY and ZSM-5, and extracting 15-149°C from the generated cracked products The light gasoline fraction is separated and injected into the second riser reactor to contact and react with the regenerated catalyst. The propylene yield of this process is 3 times (approximately 12% by weight) that of the conventional riser FCC process.

USP6222087B1 discloses a catalytic cracking method to generate light olefins. The method uses C4-C7 olefins and/or alkanes as raw materials, and adopts a catalyst with ZSM-5 or ZSM-11 as an active component. Under the reaction conditions of 20h ^-1 , the production of ethylene and propylene is increased, wherein the sum of the yields of ethylene and propylene is greater than 20% by weight, and the weight ratio of propylene to ethylene is greater than 3.0, while the yield of BTX is relatively low.

To sum up, although the prior art provides a variety of methods for increasing the production of light olefins, the increase in the yield of light olefins, especially the yield of propylene, is relatively limited, none reaching more than 30% by weight.

Contents of the invention

The purpose of the present invention is: on the basis of above-mentioned prior art, provide a kind of petroleum hydrocarbon catalytic conversion method that can greatly increase production of propylene, increase production of BTX at the same time, so that the refining process can provide more high-value chemical raw materials, thereby make the refining It is more closely integrated with the chemical process.

The method provided by the invention comprises four parts of reaction, stripping, product separation and catalyst regeneration, and is characterized in that the method comprises the following steps:

(1) Petroleum hydrocarbon feedstock is injected into the riser 1 pipe reaction zone A, contacts and reacts with the regenerant in it, and the generated reaction oil gas and catalyst mixture flows upward along the riser and enters the dense-phase bed reaction zone C;

(2) The separated C4 and/or C5 cuts from the product separation part are injected into the riser reaction zone B to contact and react with the regenerant in it, and the resulting mixture of reaction oil gas and catalyst flows upward along the riser, Enter the dense phase bed reaction zone C;

(3) The mixture of reaction oil gas and catalyst from riser reaction zone A and the mixture of reaction oil gas and catalyst from riser reaction zone B merge in dense phase bed reaction zone C, and continue in dense phase bed reaction C to react;

(4) Separating reaction oil gas and the catalyst of coke deposition after reaction, the reaction oil gas is sent to the product separation part, and the catalyst of reaction coke deposition is stripped and regenerated, and returned to the reaction part for recycling.

Compared with the prior art, the beneficial effects of the present invention are mainly reflected in the following aspects:

1. The method provided by the present invention uses heavy petroleum hydrocarbons as raw materials and relies on mature FCC technology to provide a large amount of ethylene, propylene and BTX for chemical processes. Among them, the yield of propylene can reach 25-35% by weight or higher, the yield of ethylene can reach 10-14% by weight or higher, and the yield of BTX can reach about 10% by weight.

2. The content of aromatics in the gasoline produced by the present invention is greatly increased, which can make up for the loss of octane number caused by the reduction of olefins in gasoline, so that the octane number of gasoline can be maintained at a relatively high level or to a certain extent. improve. In addition, the increase in the content of aromatics in gasoline can also provide more potential content of aromatics for the catalytic reforming process. Aromatics in gasoline are mainly C6-C8 fractions, so it is mainly BTX.

3. The present invention can be applied to all FCCUs, including conventional FCC, RFCC, DCC, MGG, ARGG, MGD, etc., and the present invention can be implemented by modifying the reaction part of the existing catalytic cracking unit. Therefore, the investment is small, the transformation period is short, and the recovery is fast, which is favorable for popularization and use. The invention can also be used in new catalytic converters.

Description of drawings

Fig. 1 is a schematic flow chart of the method provided by the present invention.

Detailed ways

equipment

The method provided by the invention includes four parts: reaction, steam stripping, product separation and catalyst regeneration, and the functions of each part are similar to the conventional FCC process. Wherein said reaction part mainly comprises riser reaction zone A, riser reaction zone B and dense-phase bed reaction zone C, in addition, also includes the settling section and oil agent rapid separation equipment positioned at the top of dense-phase bed reaction zone C, For example, cyclones. The present invention has no special requirements for the arrangement of the riser reaction zone A, the riser reaction zone B and the dense-phase bed reaction zone C, which can be designed according to the device design requirements of the conventional FCC process. The design requirements of the steam stripping, product separation and catalyst regeneration parts of the present invention are also the same as those of the conventional FCC process, as long as the C4 and C5 cuts can be separated from the product oil and gas, and they are sent to the reaction part for reaction That's it.

In the method provided by the present invention, the riser reaction zone A and the riser reaction zone B communicate with the dense-phase bed reaction zone C. The present invention has no special requirements for the arrangement of the riser reaction zone A, the riser reaction zone B and the dense-phase bed reaction zone C. For example, the riser reaction zone A and the dense-phase bed reaction zone C can be coaxially arranged and fixedly connected, while the riser reaction zone B and the dense-phase bed reaction zone C are non-coaxially arranged, but are fixedly connected; otherwise Likewise, that is, the positions of reaction zone A and reaction zone B may be interchanged. It is also possible to make the riser reaction zone A, the riser reaction zone B and the dense bed reaction zone C non-coaxial, but fixedly connected to each other.

In the method provided by the present invention, it is preferable to add a cooling agent storage tank next to the regenerator, so that the regenerated catalyst first flows through the tank, and then is sent to the riser reaction zone. The purpose of the cooling tank is to effectively control the temperature of the catalyst sent to the reaction zone of the riser. One, two or more of the cooling tanks can be provided.

In the method provided by the present invention, the density of the catalyst in the dense-phase bed reaction zone C is 100-500 kg/ ^m3 , preferably 150-400 kg/ ^m3 . The average temperature of the catalyst in the cooling tank is 500-700°C, preferably 560-650°C.

catalyst

The present invention is suitable for conventional catalytic cracking catalysts, that is, solid acid catalysts. It can be 100% amorphous silica-alumina, but it is best to include molecular sieve active components and porous high-temperature resistant substrates, such as silicon dioxide (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), clay and its mixture etc. The total content of molecular sieve in the catalyst is generally 10-50% by weight, and the rest is matrix and binder. Molecular sieve active components are usually Y-type zeolites, including REY, REHY, ultra-stable Y with different silicon-aluminum ratios, high-silicon Y, etc. The molecular sieve may also contain rare earths, and the content of rare earths may be 0.1-10% by weight. The active component preferably contains a mixture of one or more zeolites in the series of zeolites, ZSM-5 series zeolites, beta zeolites, and phosphorus aluminum zeolites and Y-type zeolites.

In addition, various catalytic cracking aids are also suitable for use in the present invention. The auxiliary agent can be added to the device separately, or the auxiliary agent component can be added during the preparation of the catalyst. The auxiliary agent can be a component that improves the selectivity of low-carbon olefins, such as shape-selective molecular sieves ZRP, ZSM-5, ZSM-11, ZSM-2, ZSM-21, TEA mordenite, etc., and the above-mentioned molecular sieves that have been modified by ion exchange , Ion exchange modification can use H, Cr, ZR, MN, CE, LA and so on. Molecular sieve components are loaded on the carrier containing Al ₂ O ₃ , Al ₂ O ₃ -SiO ₂ , kaolin, as a separate additive, or mixed into the main catalyst in the form of components when preparing general catalytic cracking catalysts, and made into a catalyst containing Catalysts for auxiliary ingredients. For a more detailed description of ZRP zeolite, see CN1058382A; for a more detailed description of ZSM-5, see USP3702886; for a more detailed description of ZSM-11, see USP3709979; for a more detailed description of ZSM-12, see USP3832449; See USP4076842 for a more detailed description of 23 and US Patent Application 130442 for a more detailed description of TEA.

petroleum hydrocarbon feedstock

In the method provided by the present invention, the petroleum hydrocarbon raw material injected into the riser reaction zone A is selected from: straight-run gas oil, coker gas oil, deasphalted oil, hydrorefined oil, hydrocracking tail oil, vacuum residue One or more mixtures of oil, atmospheric residue or crude oil, preferably straight-run wax oil or hydrocarbon oil fractions with comparable physical and chemical properties to straight-run wax oil, for example, VGO with high alkane content, VGO with high alkane content One or more mixtures of AGO, raffinate with high hydrogen content and high saturated hydrocarbon content, naphtha, and hydrotreated wax oil, and the preferred petroleum hydrocarbon raw material is wax with UOPK ≥ 12.5 Oil.

In the method provided by the present invention, the C4 and/or C5 cuts injected into the riser reaction zone B can include both C4 and/or C5 olefins and C4 and/or C5 alkanes; among them, C4 cuts are preferred. The C4 and/or C5 cuts can be produced from catalytic cracking units using the method of the present invention, or from C4 and C5 cuts from other oil refining and/or chemical processes, or from the above two sources of raw materials mixture.

Reaction conditions

In the method provided by the present invention, the reaction conditions in the riser reaction zone A are basically the same as the conventional catalytic cracking reaction conditions. Wherein, the temperature at which the regenerant enters the reaction zone A of the riser is 580°C-700°C, the reaction time is 2-10 seconds, the agent-oil ratio is 3-30, and the weight ratio of water vapor to hydrocarbon oil raw material is 0.02-0.40 , The reaction pressure is 130-450kPa. The preferred reaction conditions are as follows: the temperature at which the regenerant enters the reaction zone A of the riser is 620°C-650°C, the reaction time is 2.5-8.0 seconds, the ratio of agent to oil is 4-15, and the weight ratio of water vapor to hydrocarbon oil is 0.15 -0.30, the reaction pressure is 200-400kPa.

In the method provided by the present invention, the reaction conditions of the riser reaction zone B are as follows: the temperature at which the regeneration agent enters the riser reaction zone B is 550°C-750°C, the reaction time is 1-8 seconds, and the agent-oil ratio is 10-40 , the weight ratio of water vapor to hydrocarbon oil raw material is 0.02-0.40, and the reaction pressure is 100-500kPa. The preferred reaction conditions are as follows: the temperature at which the regenerant enters the riser reaction zone B is 590°C-690°C, the reaction time is 2.5-7.0 seconds, the agent-to-oil ratio is 13-25, and the weight ratio of water vapor to hydrocarbon oil is 0.15 -0.40, the reaction pressure is 150-300kPa.

In the method provided by the present invention, the reaction conditions of the dense-phase bed reaction zone C are as follows: the reaction temperature is 500°C-700°C, preferably 560°C-660°C; the reaction pressure is normal pressure-300 kPa, preferably is 100-230 kPa; the weight hourly space velocity is 0.5-6.0 h ^-1 , preferably 1-4 h ^-1 ; the weight ratio of catalyst to hydrocarbon oil raw material is 10-150, preferably 20-80; water vapor The weight ratio to hydrocarbon oil feedstock is 0.05-0.80:1; preferably 0.1-0.3:1. The reaction oil gas and catalyst mixture from the riser reaction zone A and B respectively enter the dense bed reaction zone C and continue to contact and react, so that the reaction depth is further improved, and a large amount of gas is injected into the dense bed reaction zone Water vapor to reduce the partial pressure of hydrocarbon oil.

In the method provided by the present invention, the pre-lift medium used at the bottom of the riser reaction zone A and the riser reaction zone B is dry gas and/or steam.

In the method provided by the present invention, there is no special requirement for the catalyst stripping part, and conventional stripping methods and equipment and improved stripping methods and equipment are applicable to the present invention. There is no special requirement for the regeneration part of the catalyst, conventional regeneration methods and equipment and improved regeneration methods and equipment are applicable to the present invention.

In the method provided by the present invention, the catalyst after stripping is sent to the regenerator to be burnt for regeneration, and the regenerated catalyst is preferably first entered into the cooling agent storage tank arranged next to the regenerator, through the method of direct or indirect heat exchange The temperature of the regenerant is lowered, for example, to 580-700°C, and then returned to the reaction part for recycling. In the method of the present invention, preferably, the regenerated catalyst first enters the cooling agent storage tank, and then returns to the reaction part for recycling. The method of the present invention is further preferably that the regenerated catalyst first enters the cooling storage tank, and then returns to the reaction part for recycling, and the temperature of the regenerated catalyst returning to the riser reaction zone A and the riser reaction zone B is different, for example, returning to the riser The temperature of the regenerated catalyst in tube reaction zone A is 10-50°C higher than the temperature of the regenerated catalyst returning to riser reaction zone B. When the temperature of the regenerated catalyst returned to riser reaction zone A and riser reaction zone B is different, it is better to set up two cooling agent storage tanks.

product

The method provided by the invention can effectively increase the production of low-carbon olefins such as ethylene and propylene, and the effect of increasing the production of propylene is particularly obvious. The content of propylene can reach more than 35% by weight or higher. At the same time, the method can also increase the production of BTX.

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.

As shown in Figure 1, the pre-lift steam 4 enters from the pre-lift section at the bottom of the riser reaction zone A, and drives the regenerated catalyst to accelerate upward along the riser; the petroleum hydrocarbon raw material 1 is atomized by the atomizing steam 2 and then injected into it through the nozzle 3 Riser reaction zone A is in contact with the catalyst and moves upward and reacts together. The C4-C5 fraction 27 cut from the liquefied gas 20 and gasoline 21, the C4-C5 fraction is lifted by the pre-lift steam 39 and then enters the bottom of the riser reaction zone B to contact with the catalyst and move upwards and react, and finally reacts with the catalyst from the riser The oil gas and catalyst in zone A enter the bottom of the dense-phase bed reaction zone C at the lower part of the settler together, and the oil gas and catalyst continue to contact and react. The steam 7 enters the annular steam distribution pipe 9 at the bottom of the dense-phase bed reaction zone C at the lower part of the settler 10 to ensure the fluidization of the dense-phase bed reaction zone C and reduce the partial pressure of oil and gas in the reaction zone. The carbon-deposited catalyst in the settler that entrains a certain amount of oil and gas flows downward through the herringbone baffle 6 of the stripper 8, and the stripping steam 5 strips the standby agent at the herringbone baffle, stripping the standby The reaction oil and gas carried by the raw agent, after stripping, the oil and gas and the catalyst pass through the rough cyclone separators 12 and 15 successively to realize the preliminary separation of the catalyst and the oil and gas. The oil and gas continue to enter the secondary cyclone separators 13 and 14, and the oil and gas that go out of the secondary cyclone separators 13 and 14 continue to enter the gas collection chamber 16, and the fine powder catalyst entrained in the crude cyclone separator oil and gas passes through the secondary cyclone separators 13 and 14. After 14, the fine powder catalyst is returned to the settler by the dipleg. The stripped spent catalyst enters the regenerator 29 through the inclined pipe 11, and the main air 30 enters the regenerator to burn off the coke on the spent catalyst and regenerate the deactivated catalyst. The completely regenerated catalyst flows into the cooling storage tank 33 through the pipeline 32, and the fluidizing wind 36 is introduced through the fluidizing wind distribution plate 35 at the bottom of the cooling storage tank to fluidize the regenerated catalyst, and the steam generator 34 makes the cooling storage tank The regenerant in the tank cools down. A part of the regenerated catalyst that has been cooled for a short time is circulated back to the bottom of the riser reaction zone A through the inclined pipe 37, and another part of the regenerated catalyst that has been cooled for a relatively long time flows into the bottom of the riser reaction zone B through the inclined pipe 38 for recycling. Flue gas 31 enters the hood. The oil and gas in the gas collection chamber 16 passes through the large oil and gas pipeline 17 and enters the subsequent separation system 18, where the products are divided into dry gas 19, liquefied gas 20, gasoline 21, diesel oil 22, heavy cycle oil 23, clarified oil 24 and external oil slurry 25. Part of the liquefied gas 20 gasoline 21 is cut into C4-C5 fraction 27 and C6+gasoline 28 by the separation device 26, and the C4-C5 fraction 26 is returned to the riser reaction zone B for reaction.

The following examples will further illustrate the method provided by the present invention, but the present invention is not limited thereto.

Example 1

This example shows that the method provided by the invention can significantly increase the yield of propylene, and at the same time increase the content of BTX in gasoline products.

The test was carried out on a medium-sized catalytic conversion device modified according to the method of the present invention, and the structure diagram of the reaction and regeneration part is shown in Fig. 1 . The physicochemical properties of the petroleum hydrocarbon raw materials used in the test are shown in raw material a in Table 1. The catalyst used was industrially produced by the Catalyst Factory of Qilu Petrochemical Branch of China Petroleum and Chemical Corporation, and the trade name was RMP. The physical and chemical properties are shown in Table 2. See feedstock A in Table 3 for the weight composition of the C4 fraction used. The main operating conditions and product conditions are shown in Table 4.

The test procedure is as follows: the raw material a in Table 1 is preheated and injected into the reaction zone A of the riser to contact and react with the regenerant in it, and the resulting reaction oil gas and catalyst mixture flows upward along the riser and enters the dense phase bed layer reaction zone C. The raw material A in Table 3, that is, the C4 fraction is injected into the riser reaction zone B, contacts and reacts with the regenerant in it, and the resulting reaction oil gas and catalyst mixture flows upward along the riser and enters the dense-phase bed reaction zone C. The reaction oil gas and catalyst mixture from the riser reaction zone A and the reaction oil gas and catalyst mixture from the riser reaction zone B meet in the dense bed reaction zone C, and continue to react under the dense bed reaction atmosphere. Separating reaction oil gas and catalyst with coke deposition after reaction, reaction oil gas is sent to the product separation part, and catalyst with carbon deposition after reaction is stripped and regenerated, and returned to the reaction part for recycling.

As can be seen from the product distribution data in Table 4, the yield of ethylene is about 10% by weight; the yield of propylene is about 35% by weight; the yield of BTX is about 10% by weight;

Example 2

This example shows that the method provided by the invention can significantly increase the yield of propylene, and at the same time increase the content of BTX in gasoline products.

The test was carried out on a medium-sized catalytic conversion device modified according to the method of the present invention, and the structure diagram of the reaction and regeneration part is shown in Fig. 1 . The physicochemical properties of the petroleum hydrocarbon raw materials used in the test are shown in Table 1, raw material b. The catalyst used is the same as in Example 1. See feedstock B in Table 3 for the weight composition of the C5 fraction used. The main operating conditions and product conditions are shown in Table 5.

The test procedure is as follows: the raw material b in Table 1 is preheated and then injected into the reaction zone A of the riser to contact and react with the regenerant in it, and the resulting reaction oil gas and catalyst mixture flows upward along the riser and enters the dense phase bed layer reaction zone C. The raw material B in Table 3, that is, the C5 fraction is injected into the riser reaction zone B, contacts and reacts with the regenerant in it, and the resulting reaction oil gas and catalyst mixture flows upward along the riser and enters the dense-phase bed reaction zone C. The reaction oil gas and catalyst mixture from the riser reaction zone A and the reaction oil gas and catalyst mixture from the riser reaction zone B meet in the dense bed reaction zone C, and continue to react under the dense bed reaction atmosphere. Separating reaction oil gas and catalyst with coke deposition after reaction, reaction oil gas is sent to the product separation part, and catalyst with carbon deposition after reaction is stripped and regenerated, and returned to the reaction part for recycling.

As can be seen from the product distribution data in Table 5, the yield of ethylene is between 7.68-12.52% by weight; the yield of propylene is about 30% by weight; the yields of ethylene and propylene are significantly lower than in Example 2 . Because the amount of C5 is very small.

Example 3

This example shows that the method provided by the invention can significantly increase the yield of propylene, and at the same time increase the content of BTX in gasoline products.

The test was carried out on a medium-sized catalytic conversion device modified according to the method of the present invention, and the structure diagram of the reaction and regeneration part is shown in Fig. 1 . The physicochemical properties of the petroleum hydrocarbon raw materials used in the test are shown in Table 1, raw material b. The catalyst used is the same as in Example 1. See feedstock C in Table 3 for the weight composition of the C4-C5 cuts used. The main operating conditions and product conditions are shown in Table 6.

The test procedure is as follows: the raw material b in Table 1 is preheated and then injected into the reaction zone A of the riser to contact and react with the regenerant in it, and the resulting reaction oil gas and catalyst mixture flows upward along the riser and enters the dense phase bed layer reaction zone C. The raw material C in Table 3, that is, the C4-C5 fraction is injected into the riser reaction zone B, contacts and reacts with the regenerant in it, and the resulting reaction oil gas and catalyst mixture flows upward along the riser and enters the dense-phase bed reaction zone c. The reaction oil gas and catalyst mixture from the riser reaction zone A and the reaction oil gas and catalyst mixture from the riser reaction zone B meet in the dense bed reaction zone C, and continue to react under the dense bed reaction atmosphere. Separating reaction oil gas and catalyst with coke deposition after reaction, reaction oil gas is sent to the product separation part, and catalyst with carbon deposition after reaction is stripped and regenerated, and returned to the reaction part for recycling.

As can be seen from the product distribution data in Table 6, the productive rate of ethylene, propylene, and BTX has increased compared with that of Example 1.

Comparative example 1

This comparative example adopts the method described in USP5,846,403, and utilizes the petroleum hydrocarbon feedstock and catalyst described in Example 1 to carry out the test results obtained.

See Table 7 for main operating conditions and product distribution. It can be seen from Table 7 that the yields of ethylene, propylene and BTX are greatly improved by adopting the method of the present invention compared with the method described in the comparative example USP5,846,403, and qualitative changes have taken place.

Comparative example 2

This comparative example adopts the method described in WO00/40672, and utilizes the petroleum hydrocarbon feedstock and the catalyst described in Example 1 to carry out the test results obtained.

See Table 8 for main operating conditions and product distribution. It can be seen from Table 8 that by adopting the method of the present invention, the yields of ethylene, propylene, and BTX are greatly improved compared with the method described in WO00/40672, and qualitative changes have taken place.

Table 1

Raw oil name Daqing VGO   VGO after hydrogenation Raw oil label Raw material a Raw material b Density, g/ ^cm3 0.8764 0.8836 Kinematic viscosity, mm ² /s 80℃ 20.39 24.2 100°C 12.06 - freezing point, ℃ ＞50 31 Aniline point, ℃ 117.7 - Carbon residue, m% 0.93 0.61 Basic nitrogen, ppm 412 100 Elemental composition, weight % C 86.70 86.85 h 13.48 13.23 S 0.13 0.041 N 0.13 0.01 Family composition, weight % saturated hydrocarbon 75.0 77.4 Aromatics 19.8 20.2 colloid 5.2 2.4 Asphaltenes ＜0.1 ＜0.05 Distillation range, ℃ initial boiling point 246 267 5% 402 373 10% 430 399 30% 482 429 50% 519 449 70% 573 (75.2%) 464 Distillation volume (350C), % 1.5 1.3 Distillation volume (500C), % 39.4 45.9 Liquid temperature > 400°C, % 61.6(538C) -

Table 2

Analysis Project RMP Al ₂ O ₃ content 50.1 Fe ₂ O ₃ content 0.44 Na ₂ O content 0.054 Ignition loss, % 11.8 Pore volume 0.28 specific surface area 204 Heap Ratio (ABD) 0.79 wear index 1.4 microreactivity 76 Particle size distribution 15.890.576.9

table 3

Composition of C4-C5 fractions   Raw material A   Raw material B   Raw material C Isobutane 14.29 0.00 14.87 n-Butane 6.32 0.00 6.89 Butene-1 13.82 0.00 13.00 Isobutylene 33.03 0.00 31.51 trans-butene-2 18.60 0.00 17.2 cis-butene-2 13.69 0.00 13.23 Butadiene-1,3 0.25 0.00 0.29  N-alkane C5 0.00 6.3 0.19 Isoparaffin C5 0.00 7.9 0.24 Olefin C5 0.00 85.8 2.58 Total 100.00 100.00 100.00

Table 4

Riser reaction zone A: Regenerant enters, ℃ 580 620 650 Response time, seconds 3 4 6 Agent oil ratio 5 10 15 Water injection (accounting for raw material), wt% 10 10 10 Riser reaction zone B: Regenerant enters, ℃ 590 640 690 Response time, seconds 2.5 4 6 Agent oil ratio 15 20 25 Water injection (accounting for raw material), wt% 5 5 5 Dense bed reaction zone C: Reaction temperature, ℃ 580 580 580 Reaction pressure, kPa 260 260 260 Agent oil ratio 25 50 65 Weight hourly space velocity, 1/h 2 3 4 Water injection (accounting for raw material), wt% 10 10 10  Material balance, weight % dry gas 17.90 20.86 24.10 Liquefied gas 47.82 48.63 46.69 C ₅ ⁺ gasoline 18.5 16.17 15.39 diesel fuel 5.86 4.42 3.35 heavy oil 2.47 2.0 1.48 Coke 7.45 7.92 8.99 Total 100.00 100.00 100.00 Conversion rate, weight % Ethylene yield, weight % 11.42 12.4 13.7 Propylene yield, weight % 35.64 36.01 34.89 stupid, heavy % 1.45 1.67 1.89 Toluene, wt% 2.44 2.83 3.50 Xylene, wt% 7.38 8.01 9.20

table 5

Riser reaction zone A: Regenerant enters, ℃ 580 620 650 Response time, seconds 3 4 6 Agent oil ratio 5 10 15 Water injection (accounting for raw material), wt% 10 10 10 Riser reaction zone B: Regenerant enters, ℃ 590 640 690 Response time, seconds 2.5 4 6 Agent oil ratio 15 20 25 Water injection (accounting for raw material), wt% 5 5 5 Dense bed reaction zone C: Reaction temperature, ℃ 580 580 580 Reaction pressure, kPa 260 260 260 Agent oil ratio 25 50 65 Weight hourly space velocity, 1/h 2 3 4 Water injection (accounting for raw material), wt% 10 10 10  Material balance, weight % dry gas 12.38 16.37 23.05 Liquefied gas 54.96 53.62 49.23 C ₅ ⁺ petrol 18.69 16.72 13.65 diesel fuel 4.76 4.12 3.44 heavy oil 3.20 2.80 2.28 Coke 6.02 6.36 8.36 Total 100.00 100.00 100.00 Conversion rate, weight % Ethylene yield, weight % 7.68 10.27 12.52 Propylene yield, weight % 29.48 31.15 30.65 stupid, heavy % 1.05 1.23 1.50 Toluene, wt% 2.21 2.39 3.18 Xylene, wt% 6.89 7.01 8.20

Table 6

Riser reaction zone A: Regenerant enters, ℃ 580 620 650 Response time, seconds 3 4 6 Agent oil ratio 5 10 15 Water injection (accounting for raw material), wt% 10 10 10 Riser reaction zone B: Regenerant enters, ℃ 590 640 690 Response time, seconds 2.5 4 6 Agent oil ratio 15 20 25 Water injection (accounting for raw material), wt% 5 5 5 Dense bed reaction zone C: Reaction temperature, ℃ 580 580 580 Reaction pressure, kPa 260 260 260 Agent oil ratio 25 50 65 Weight hourly space velocity, 1/h 2 3 4 Water injection (accounting for raw material), wt% 10 10 10  Material balance, weight % dry gas 18.02 21.25 24.3 Liquefied gas 48.67 49.31 47.14 C ₅ ⁺ gasoline 17.47 15.01 14.9 diesel fuel 5.86 4.42 3.32 heavy oil 2.47 2.0 1.42 Coke 7.51 8.01 8.92 Total 100.00 100.00 100.00 Conversion rate, weight % Ethylene yield, weight % 11.81 13.01 14.18 Propylene yield, weight % 35.98 36.81 34.95 stupid, heavy % 1.46 1.67 1.90 Toluene, wt% 2.51 2.84 3.50 Xylene, wt% 7.58 8.21 9.40

Table 7

Riser reaction zone A: Comparative example this invention Regenerant enters, ℃ 580 620 Response time, seconds 3 3 Agent oil ratio 10 15 Water injection (accounting for raw material), wt% 10 10 Riser reaction zone B: Regenerant enters, ℃ / 640 Response time, seconds / 4 Agent oil ratio / 20 Water injection (accounting for raw material), wt% / 5 Dense bed reaction zone C: Reaction temperature, ℃ / 580 Reaction pressure, kPa / 260 Agent oil ratio / 50 Weight hourly space velocity, 1/h / 4 Water injection (accounting for raw material), wt% / 10  Material balance, weight % dry gas 8.90 21.25 Liquefied gas 15.82 49.31 C ₅ ⁺ petrol 36.11 15.01 diesel fuel 7.60 4.42 heavy oil 25.40 2.0 coke 6.17 8.01 Total 100.00 100.00 Conversion rate, weight % Ethylene yield, weight % 1.7 13.01 Propylene yield, weight % 5.45 36.81 Benzene, weight % 0.89 1.67 A stupid weight % 2.1 2.84 Dimethicone, weight% 4.2 8.21

Table 8

Riser reaction zone A: Comparative example This method Regenerant enters, ℃ 620 620 Response time, seconds 3 3 Agent oil ratio 10 15 Water injection (accounting for raw material), wt% 10 10 Riser reaction zone B: Regenerant enters, ℃ 640 640 Response time, seconds 4 4 Agent oil ratio 20 20 Water injection (accounting for raw material), wt% 5 5 Dense bed reaction zone C: Reaction temperature, ℃ - 580 Reaction pressure, kPa - 260 Agent oil ratio - 50 Weight hourly space velocity, 1/h - 4 Water injection (accounting for raw material), wt% 10  Material balance, weight % dry gas 5.4 21.25 Liquefied gas 29.6 49.31 C ₅ ⁺ gasoline 27.9 15.01 diesel fuel 17.7 4.42 heavy oil 13.5 2.0 Coke 5.9 8.01 Total 100.00 100.00 Conversion rate, weight % Ethylene yield, weight % 3.6 13.01 Propylene yield, weight % 14.1 36.81 Benzene, weight % 1.01 1.67 Toluene, wt% 1.98 2.84 Dimethicone, weight% 4.01 8.21

Claims (19)

1, a kind of method for catalytic conversion of petroleum hydrocarbon comprises reaction, stripping, product separation and catalyst regeneration four parts, it is characterized in that this method may further comprise the steps:

(1) petroleum hydrocarbon raw material injecting lift tube reaction district A contacts, reacts with regenerator in it, and reaction oil gas that is generated and mixture of catalysts upwards flow along this riser tube, enter dense-phase bed reaction zone C;

(2) C4 and/or C 5 fraction injecting lift tube reaction district B contact, react with regenerator in it, and reaction oil gas that is generated and mixture of catalysts upwards flow along this riser tube, enter dense-phase bed reaction zone C;

(3) converge at dense-phase bed reaction zone C from the reaction oil gas of riser reaction zone A and mixture of catalysts and from reaction oil gas and the mixture of catalysts of riser reaction zone B, and continue in dense-phase bed reaction C, to react;

(4) catalyzer of separating reaction oil gas and reaction back carbon deposit, reaction oil gas is sent into the product separation part, and the catalyzer of reaction back carbon deposit returns reactive moieties and recycles after stripping, regeneration.

2, according to the method for claim 1, it is characterized in that described riser reaction zone A and the coaxial setting of dense-phase bed reaction zone C, and fixedly connected, and riser reaction zone B and the non-coaxial setting of dense-phase bed reaction zone C, and fixedly connected; Perhaps described riser reaction zone B is coaxial setting, also fixedlys connected with dense-phase bed reaction zone C, and riser reaction zone A and the non-coaxial setting of dense-phase bed reaction zone C, but be fixedly connected; Perhaps described riser reaction zone A and riser reaction zone B and dense-phase bed reaction zone C are non-coaxial setting, but connection fixed to one another.

3, according to the method for claim 1, it is characterized in that the other cooling storage jar of setting up of described revivifier, make catalyzer after the regeneration this jar of flowing through earlier, and then deliver to riser reaction zone A and riser reaction zone B.

4,, it is characterized in that described cooling storage jar is one, two or more, and the medial temperature of cooling storage jar inner catalyst is 500-700 ℃ according to the method for claim 3.

5,, it is characterized in that the medial temperature of described cooling storage jar inner catalyst is 560-650 ℃ according to the method for claim 1.

6,, it is characterized in that described activity of such catalysts component is selected from one or more zeolites in this group zeolite of ZRP series zeolite, ZSM-5 series zeolite, β zeolite, phosphorus aluminium zeolite and the mixture of y-type zeolite according to the method for claim 1.

7,, it is characterized in that the petroleum hydrocarbon raw material of described injecting lift tube reaction district A is selected from: the mixture of one or more in straight-run gas oil, wax tailings, deasphalted oil, hydrofined oil, hydrocracking tail oil, vacuum residuum, long residuum or the crude oil according to the method for claim 1.

8,, it is characterized in that the petroleum hydrocarbon raw material of described injecting lift tube reaction district A is selected from: the wax oil of straight-run gas oil, the wax oil after hydrotreatment or UOPK 〉=12.5 according to the method for claim 7.

9, according to the method for claim 1, the petroleum hydrocarbon that it is characterized in that described injecting lift tube reaction district B is a C 4 fraction.

10, according to the method for claim 1, it is characterized in that the reaction conditions of described riser reaction zone A is as follows: the temperature that regenerator enters riser reaction zone A is that 580 ℃-700 ℃, reaction times are that 2-10 second, agent-oil ratio are that the weight ratio of 3-30, water vapor and hydrocarbon oil crude material is that 0.02-0.40, reaction pressure are 130-450kPa.

11, according to the method for claim 10, it is characterized in that the reaction conditions of described riser reaction zone A is as follows: the temperature that regenerator enters riser reaction zone A is that 620 ℃-650 ℃, reaction times are that 2.5-8.0 second, agent-oil ratio are that the weight ratio of 4-15, water vapor and hydrocarbon oil crude material is that 0.15-0.30, reaction pressure are 200-400kPa.

12, according to the method for claim 1, it is characterized in that the reaction conditions of described riser reaction zone B is as follows: the temperature that regenerator enters riser reaction zone B is that 550 ℃-750 ℃, reaction times are that 1-8 second, agent-oil ratio are that the weight ratio of 10-40, water vapor and hydrocarbon oil crude material is that 0.02-0.40, reaction pressure are 100-500kPa

13, according to the method for claim 12, it is characterized in that the reaction conditions of described riser reaction zone B is as follows: the temperature that regenerator enters riser reaction zone B is that 590 ℃-690 ℃, reaction times are that 2.5-7.0 second, agent-oil ratio are that the weight ratio of 13-25, water vapor and hydrocarbon oil crude material is that 0.15-0.40, reaction pressure are 150-300kPa.

14, according to the method for claim 1, it is characterized in that the reaction conditions of described dense-phase bed reaction zone C is as follows: temperature of reaction is that 500 ℃-700 ℃, reaction pressure are that normal pressure-300 kPa, weight hourly space velocity are 0.5-6.0 hour ^-1, catalyzer and hydrocarbon oil crude material weight ratio be that the weight ratio of 10-150, water vapor and hydrocarbon oil crude material is 0.05-0.80: 1.

15, according to the method for claim 14, it is characterized in that the reaction conditions of described dense-phase bed reaction zone C is as follows: temperature of reaction is that 560 ℃-660 ℃, reaction pressure are that 100-230 kPa, weight hourly space velocity are 1-4 hour ^-1, catalyzer and hydrocarbon oil crude material weight ratio be that the weight ratio of 20-80, water vapor and hydrocarbon oil crude material is 0.1-0.3: 1.

16,, it is characterized in that the catalyzer after the described regeneration is introduced into cooling storage jar, and then return reactive moieties and recycle, and it is different with the temperature of the regenerated catalyst of riser reaction zone B to return riser reaction zone A according to the method for claim 1.

17, according to the method for claim 16, the temperature that it is characterized in that the described regenerated catalyst that returns riser reaction zone A is than the high 10-50 of temperature ℃ of the regenerated catalyst that returns riser reaction zone B.

18, according to the method for claim 1, it is characterized in that the C4 of described injecting lift tube reaction district B and/or C 5 fraction are from the catalytic cracking unit of using the method for the invention, perhaps from other oil refining and/or chemical process, or the mixture of the raw material in above-mentioned two kinds of sources.

19,, it is characterized in that described activity of such catalysts component is a y-type zeolite according to the method for claim 1.

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