CN1282734C - An effective process for the catalytic conversion of C4 hydrocarbons - Google Patents

Abstract

The present invention provides an effective process for the catalytic conversion of C4 hydrocarbons. The pre-lifting section of the catalytic gasoline upgrading auxiliary reactor or the pre-lifting section of heavy oil catalytic cracking is used as the C4 hydrocarbon catalytic conversion reactor, or in the catalytic gasoline A separate C4 hydrocarbon catalytic conversion reactor is set up before the upgrading auxiliary reactor. After C4 hydrocarbons enter the C4 hydrocarbon catalytic conversion reactor from the bottom, they are contacted and mixed with the high-temperature catalyst from the regenerator at a certain reaction temperature. and catalytic conversion reaction to generate a part of aromatics, ethylene and propylene; the reaction product and catalyst enter the catalytic gasoline upgrading auxiliary reactor or the main riser reactor for heavy oil cracking. The present invention can increase the production of aromatics and ethylene/propylene while reducing catalyst The temperature is beneficial to reduce the loss of catalytic gasoline upgrading process, or reduce the dry gas yield by reducing the reaction time of heavy oil catalytic cracking process.

Description

An effective process for the catalytic conversion of C4 hydrocarbons

technical field

The invention belongs to the technical field of catalytic conversion process of petroleum hydrocarbons, in particular, it belongs to the process of catalytic cracking of heavy oil, process of catalytic gasoline modification and reduction of olefins and effective catalytic conversion process of C4 hydrocarbons.

Background technique

A large number of C4 hydrocarbons are by-produced in the process of petroleum refining and petrochemical production, and their comprehensive utilization is a necessary means to improve the economic benefits of enterprises. However, the domestic chemical utilization rate of C4 hydrocarbons is still very low. Before the 1980s, petroleum refining, especially the C4 fraction from the catalytic cracking unit, was mainly used to produce alkylated gasoline and composite gasoline or as industrial and civil fuel; the C4 fraction obtained by steam cracking was used to remove butadiene for synthesis In addition to rubber raw materials, it is also used as fuel. Since the 1990s, due to the advancement of separation technology, the application of C4 fractions as petrochemical raw materials has developed rapidly. It is predicted that the C4 fraction will be the petrochemical raw material that may be fully utilized after ethylene and propylene.

Butadiene in the C4 mixture is very active and can be separated by extraction. Butadiene can be used as a polymerized monomer for synthetic rubber (such as butadiene rubber, neoprene, etc.) and resin (such as ABS resin), and can also be used as a raw material for the production of ethanedinitrile, sebacic acid and other products.

Isobutene is one of the most basic organic chemical raw materials, and its chemical properties are also very active. Using isobutene as a raw material, methyl tert-butyl ether required for high-octane gasoline seasoning and clean gasoline formulations can be produced by methanol etherification. The hydration reaction of isobutene by using the H+ on the cation exchange resin can produce tert-butanol. In addition, isobutylene is one of the monomers of synthetic rubber, mainly used to prepare butyl rubber and polyisobutylene rubber.

After the C4 fraction undergoes etherification process or resin hydration process to make full use of isobutene, the concentration of n-butene (including 1-butene and 2-butene) in the remaining components is already very high, and correspondingly there are various chemical utilization of n-butene way. At present, the chemical utilization rate of n-butene is very low, mainly dehydrogenation to butadiene. In addition, n-butene can also be oxidized to produce maleic anhydride and butylene oxide; dimerize to produce octene, which in turn can produce isononanol; hydroformylation to synthesize 2 methyl butanol; and Addition of anhydrous glacial acetic acid to produce sec-butyl acetate. Butene can also be oxidatively dehydrogenated to produce butadiene or isomerized to produce isobutene.

N-butane can be oxidized to produce maleic anhydride. Compared with the traditional benzene method, this method has the advantages of cheap raw materials, less pollution, and lower consumption. The process has developed rapidly since it was industrialized in the United States in 1974. With people's increasing requirements for environmental protection, the n-butane oxidation method shows stronger vitality. At present, more than 80% of the world's maleic anhydride uses the n-butane route, and there is an increasing trend.

The chemical nature of isobutane is inactive, and it is difficult to further process and utilize, so it is rarely used in chemical industry. my country is rich in C4 hydrocarbon resources, but the utilization of C4 hydrocarbons is still in its infancy. Although the refinery C4 fraction can directly enter the alkylation unit to produce high-octane alkylated gasoline or blended gasoline, the development of alkylation technology has restricted the large-scale utilization of C4 hydrocarbons; at the same time, domestic chemical utilization China's production technology, product variety and development of downstream products are still far behind industrial developed countries, and most of the C4 hydrocarbons are burned directly as fuel. With the smooth implementation of my country's "West-to-East Gas Pipeline" project, the C4 fraction used as fuel will depreciate severely, which will have a huge impact on the entire petrochemical enterprise and pose a huge challenge to petrochemical enterprises. Therefore, the rational use of C4 hydrocarbon resources and the improvement of their chemical utilization rate will not only make rational use of resources, but also benefit the development of my country's chemical industry, and will play a decisive role in enhancing the international competitiveness of Chinese petrochemical enterprises after joining the World Trade Organization. role.

At the same time, with the increasingly stringent environmental protection requirements, my country has made major adjustments to gasoline standards. In December 1999, the National Environmental Protection Agency formulated the "Standards for Hazardous Substances in Motor Gasoline", requiring gasoline olefin content≯35(v)%, octane number (research method)≮90, aromatics content≯40(v)%, sulfur content ≯800ppm, stipulated that it will be implemented nationwide from January 1, 2003. It is expected that after 2005, especially as the "Green Olympics" in 2008 is approaching, more stringent standards will be implemented for gasoline quality.

At present, catalytic cracking gasoline is still the main gasoline used in vehicles, and some data show that catalytic cracking gasoline accounts for as high as 85% of the finished gasoline. The volume fraction of olefins in FCC gasoline is 45%-55%, which is much higher than the gasoline standard of the new formula. Therefore, reducing the olefin content in catalytically cracked gasoline has become an urgent task in the current oil refining industry. Since the refinery processes paraffin-based crude oil, its gasoline octane number (research method) is generally 89-90, which barely meets the standard. If the olefin content is greatly reduced, the octane number will inevitably fail to meet the requirements. How to meet the requirement that the olefin content in gasoline is not more than 35(v)% and ensure that the octane number reaches the standard has become a very urgent and very difficult problem.

Contents of the invention

The technical problem to be solved by the present invention is to provide an effective reaction process for the catalytic conversion of C4 hydrocarbons. The present invention does not need to carry out large Change, choose the appropriate refining inlet and structure, make C4 hydrocarbons contact with high-temperature catalytic cracking catalyst, and carry out effective catalytic conversion reaction, so as to increase the production of aromatics and ethylene propylene.

The present invention is achieved through the following technical solutions:

An effective process for the catalytic conversion of C4 hydrocarbons. The pre-lifting section of the catalytic gasoline reforming auxiliary reactor is used as a C4 hydrocarbon catalytic conversion reactor. The regenerated high-temperature catalyst enters the C4 hydrocarbon catalytic converter from the regenerator through an inclined tube. The bottom of the conversion reactor is mixed with C4 hydrocarbons at a preheating temperature of 40-300 ° C. After the reaction temperature is 400-650 ° C, the weight ratio of catalyst to C4 hydrocarbons is 2-100, the catalyst activity is 53-70, and the reaction time is 2.0-100.0s or weight space velocity of 0.1-100hr ^-1 and reaction pressure of 0.1-0.4MPa for contact, mixing and catalytic conversion reaction to generate part of aromatics, ethylene and propylene; the reaction product and catalyst are promoted together with catalytic gasoline The reaction temperature of the distillate is 350-600°C, the preheating temperature of gasoline raw material is 40-200°C, the weight ratio of catalyst to oil is 2-20, the catalyst activity is 55-65, the reaction time is 2.0-20.0s, and the reaction pressure is 0.1- Contact, gasification, mixing and reaction are carried out at 0.4MPa; the reacted oil gas and catalyst pass through the catalytic gasoline upgrading auxiliary reactor, and at its outlet, the upgraded oil gas and catalyst are separated by a high-efficiency gas-solid rapid separation device, and the catalyst enters the settler and The stripping section enters the regenerator through the inclined pipe after being stripped by the stripping steam; after the reaction oil gas leaves the settler, it enters the oil-gas separation system.

An effective process for the catalytic conversion of C4 hydrocarbons. A separate C4 hydrocarbon catalytic conversion reactor is set up before the auxiliary reactor for catalytic gasoline upgrading. The regenerated high-temperature catalyst enters the catalytic conversion of C4 hydrocarbons from the regenerator through inclined pipes. The bottom of the reactor is mixed with C4 hydrocarbons at a preheating temperature of 40-300 ° C. After the reaction temperature is 400-650 ° C, the weight ratio of catalyst to C4 hydrocarbons is 2-100, the catalyst activity is 53-70, and the reaction time is 2.0-100.0s or the weight space velocity is 0.1-100hr ^-1 , the reaction pressure is 0.1-0.4MPa to carry out the contact, mixing and catalytic conversion reaction to generate a part of aromatics, ethylene and propylene; the reaction product and the catalyst are separated and enter the catalytic converter through the pipeline. The settler of gasoline reforming auxiliary reactor, the cracking catalyst after cooling enters the bottom of catalytic gasoline reforming auxiliary reactor and catalytic gasoline fraction at the reaction temperature of 350-600°C, gasoline raw material preheating temperature of 40-200°C, catalyst oil The weight ratio is 2-20, the catalyst activity is 55-65, the reaction time is 2.0-20.0s, and the reaction pressure is 0.1-0.4MPa to carry out contact, gasification, mixing and reaction; the reaction oil gas and the catalyst are modified by catalytic gasoline Auxiliary reactor, to its outlet, the upgraded oil gas and catalyst are separated by a high-efficiency gas-solid rapid separation device. The catalyst enters the settler and stripping section, and after being stripped by steam stripping, it enters the regenerator through the inclined tube; the reacted oil gas leaves the settler After that, it enters the oil and gas separation system.

An effective process for catalytic conversion of C4 hydrocarbons. The pre-lifting section of heavy oil catalytic cracking is used as a catalytic conversion reactor for C4 hydrocarbons. The regenerated high-temperature catalyst enters the catalytic conversion reactor of C4 hydrocarbons from the regenerator through inclined pipes. After the bottom is mixed with C4 hydrocarbons at a preheating temperature of 40-300°C, the reaction temperature is 400-650°C, the weight ratio of catalyst to C4 hydrocarbons is 2-100, the catalyst activity is 53-70, and the reaction time is 2.0-100.0 s or weight space velocity of 0.1-100hr ^-1 and reaction pressure of 0.1-0.4MPa to carry out contact, mixing and catalytic conversion reaction to generate a part of aromatics, ethylene and propylene; the reaction product and catalyst are lifted together with the heavy oil containing atomized steam The raw materials are mixed, the reaction temperature is 460-530°C, the preheating temperature of heavy oil raw materials is 160-250°C, the weight ratio of catalyst to oil is 5-8, the catalyst activity is 50-70, the reaction time is 2.5-3.0s, and the reaction pressure is Contact, gasification, mixing and reaction are carried out at 0.1-0.4MPa. Oil gas, water vapor and catalyst pass through the main riser reactor together, and the reaction oil gas is reacted by the high-efficiency gas-solid rapid separation device and the top spin of the settler at the outlet of the riser reactor. Separated from the catalyst, the catalyst enters the stripping section through the settler, and enters the regenerator after stripping. The reaction oil gas leaves the settler and enters the fractionation system for separation of rich gas, naphtha light fraction, naphtha heavy fraction, diesel oil, re-refined oil, and oil slurry.

The advantage of the process technology of the present invention is that the catalytic cracking unit is used to contact and react C4 hydrocarbons with high-temperature cracking catalysts, while increasing the production of aromatics, ethylene and propylene, and the process of catalytic gasoline upgrading and olefin reduction can reduce the catalyst temperature to facilitate upgrading The olefin reduction process is carried out and finally achieves the purpose of greatly reducing the olefin content of catalytic gasoline and the octane number without too much loss. For the heavy oil catalytic cracking reaction process, the gas velocity can be increased, and the reaction time of the heavy oil catalytic cracking process can be reduced to reduce the dry gas yield. The purpose of increasing the liquid yield can also save part of the stripping steam. This process technology not only greatly improves the utilization rate of C4 hydrocarbons at the current level, but also properly optimizes the operation of the heavy oil catalytic cracking process and the auxiliary fluidized catalytic process.

Description of drawings

Fig. 1 is a flowchart of the method of the present invention;

Fig. 2 is the flow chart that the auxiliary reactor form in Fig. 1 is changed into a riser and a turbulent bed form;

Fig. 3 is the flow chart that auxiliary reactor form is changed into turbulent bed form among Fig. 1;

Fig. 4 is the flow chart that adopts the C4 hydrocarbon catalytic conversion reactor that sets up separately;

Fig. 5 is the flow chart that the auxiliary reactor in Fig. 4 is changed into riser and adds turbulent bed form;

Fig. 6 is the flow chart that auxiliary reactor among Fig. 4 is changed into turbulent bed form;

Fig. 7 is the flowchart of realizing the method of the present invention in the riser pre-lift section of conventional heavy oil catalytic cracking unit;

Fig. 8 is a flow chart of realizing the method of the present invention in the pre-lift section of a conventional heavy oil catalytic cracking unit transformed through enlarged inner diameter;

Fig. 9 is a flowchart of simultaneously realizing the method of the present invention in the pre-lift section of the riser of a conventional heavy oil catalytic cracking unit and the auxiliary reactor for catalytic gasoline modification and olefin reduction;

Fig. 10 is the flow chart that the form of auxiliary reactor among Fig. 9 is changed into riser and adds turbulent bed form;

Fig. 11 is the flow chart that the auxiliary reactor form in Fig. 9 is changed into the turbulent bed form;

Fig. 12 is a flowchart of simultaneous catalytic upgrading of C4 hydrocarbons in the riser pre-lift section of a conventional heavy oil catalytic cracking unit and a separate C4 hydrocarbon catalytic conversion reactor;

Fig. 13 is the flow chart that the auxiliary reactor in Fig. 12 is changed into a riser and adds a turbulent bed form;

Fig. 14 is the flow chart that the auxiliary reactor in Fig. 12 is changed into the turbulent bed form;

Fig. 15 is a flow chart of simultaneously realizing the method of the present invention in the conventional heavy oil catalytic cracking unit riser pre-lift section and the catalytic gasoline modification and olefin reduction auxiliary reactor pre-lift section through the transformation of the enlarged inner diameter;

Fig. 16 is a flow chart of changing the auxiliary reactor in Fig. 15 into a riser and adding a turbulent bed form;

Fig. 17 is the flow chart that the auxiliary reactor in Fig. 15 is changed into the turbulent bed form;

Fig. 18 is a flow chart of realizing the method of the present invention simultaneously in the conventional heavy oil catalytic cracking unit riser pre-lift section and the C4 hydrocarbon catalytic conversion reactor set up separately through the expansion of inner diameter transformation;

Fig. 19 is a flow chart of changing the auxiliary reactor in Fig. 18 into a riser and adding a turbulent bed form;

Fig. 20 is a flow chart of changing the auxiliary reactor in Fig. 18 into a turbulent bed form.

Detailed ways

The starting point of the present invention is to consider that the structural characteristics of the refinery process are absolutely based on the catalytic cracking process, and almost any refinery has a catalytic cracking unit. At the same time, a large amount of C4 hydrocarbons produced by the refinery have not been fully utilized. Catalytic conversion technology enables C4 hydrocarbons to contact and react with high-temperature cracking catalysts firstly. While increasing the production of aromatics, ethylene and propylene, the process of catalytic gasoline upgrading and reducing olefins can achieve the purpose of lowering the catalyst temperature to facilitate the reaction process. For heavy oil The catalytic cracking reaction process can achieve the purpose of increasing the gas velocity and reducing the reaction time of the heavy oil catalytic cracking process, and at the same time can save a part of the pre-lifting steam.

The process flow of the present invention can be seen in Figure 1, briefly described as follows: an auxiliary riser reactor 113 for catalytic gasoline modification and olefin reduction is set up next to the original catalytic cracking unit regenerator 103, and the regenerated high-temperature catalyst enters from the regenerator 103 through an inclined pipe 111 The bottom of the pre-lift section of the auxiliary riser reactor 113 is mixed with C4 hydrocarbons 120 at a preheating temperature of 40-300°C and the reaction temperature is 400-650°C, the weight ratio of catalyst to C4 hydrocarbons is 2-100, and the catalyst The activity is 53-70, the reaction time is 2.0-100.0 or the weight space velocity is 0.1-100hr ^-1 , and the reaction pressure is 0.1-0.4MPa to carry out contact, mixing and catalytic conversion reaction to increase the production of aromatics and ethylene and propylene. The reaction product and the catalyst are promoted together with the catalytic gasoline fraction 115 at a reaction temperature of 350-600°C, a gasoline raw material preheating temperature of 40-200°C, a catalyst-oil weight ratio of 2-20, a catalyst activity of 55-65, and a reaction time of 2.0-20.0s, the reaction pressure is 0.1-0.4MPa to carry out contact, gasification, mixing and reaction, the reaction oil gas, water vapor and catalyst pass through the riser reactor 113, to its outlet by the high-efficiency gas-solid rapid separation device 116 The upgraded oil and gas are separated from the catalyst, and the catalyst enters the settler 117 and the stripping section 118 , and enters the regenerator 103 through the inclined pipe 112 after being stripped by the stripping steam 119 . After the reaction oil gas 121 leaves the settler 117, it enters the oil gas separation system.

The present invention also includes:

1, the form of auxiliary riser reactor in Fig. 1 is changed into riser and adds turbulent bed form, thus can obtain the invention flow process of Fig. 2, brief description is as follows: set up next to former catalytic cracking unit regenerator 203 and be used for catalytic gasoline degassing Auxiliary fluidized reactor 213 for olefin modification, the regenerated high-temperature catalyst enters the bottom of auxiliary fluidized reactor 213 from regenerator 203 through inclined pipe 211, and C4 hydrocarbons 220 with a preheating temperature of 40-300°C After mixing, the reaction temperature is 400-650°C, the weight ratio of the catalyst to C4 hydrocarbons is 2-100, the catalyst activity is 53-70, the reaction time is 2.0-100.0s or the weight space velocity is 0.1-100hr ^-1 , and the reaction pressure is Contact, mixing and catalytic conversion reactions are carried out at 0.1-0.4MPa to increase the production of aromatics and ethylene and propylene. The reaction product and the catalyst are lifted together with the catalytic gasoline fraction 215 at a reaction temperature of 350-600°C, a gasoline raw material preheating temperature of 40-200°C, a catalyst-to-oil weight ratio of 2-20, and a catalyst activity of 55-65. The reaction time is 1.0-20.0s, the weight space velocity of the fluidized bed part is 1-1000h ^-1 , and the reaction pressure is 0.1-0.4MPa to carry out contact, gasification, mixing and reaction, and the reaction oil gas, water vapor and catalyst pass together From the riser reactor 213, the high-efficiency gas-solid rapid separation device 216 separates the upgraded oil and gas from the catalyst at its outlet, and the catalyst enters the settler 217 and the stripping section 218, and after being stripped by the stripping steam 219, it enters regeneration through the inclined pipe 212 device 203. After the reaction oil gas 221 leaves the settler 217, it enters the oil gas separation system.

2. The form of the auxiliary riser reactor in Fig. 1 is changed to the turbulent bed form, thus the invention process of Fig. 3 can be obtained, which is briefly described as follows: set up next to the former catalytic cracking unit regenerator 303 for catalytic gasoline upgrading and reducing olefins Auxiliary fluidized reactor 313, the regenerated high-temperature catalyst enters the bottom of auxiliary fluidized reactor 313 from regenerator 303 through inclined pipe 311, and is mixed with C4 hydrocarbons 320 with a preheating temperature of 40-300° C. The reaction temperature is 400-650°C, the weight ratio of the catalyst to C4 hydrocarbons is 2-100, the catalyst activity is 53-70, the reaction time is 2.0-100.0s or the weight space velocity is 0.1-100hr ^-1 , and the reaction pressure is 0.1- Contact, mixing and catalytic conversion reactions are carried out at 0.4MPa to increase the production of aromatics and ethylene and propylene. The reaction product and the catalyst go together into the lifting auxiliary fluidized reactor 313 to form a reaction bed 316. The upper nozzle of the catalyst riser is on the top of the reaction bed 316, and the FCC gasoline fraction 317 containing atomized steam enters the auxiliary flow through the nozzle. The lower part of the state reactor bed 316 contacts, gasifies, mixes and reacts with the catalyst in the bed 316. In the reaction bed 316 of the auxiliary fluidized reactor 313, the reaction temperature is maintained at 350-600°C, the raw material preheating temperature is 40-300°C, the catalyst activity is 50-70, and the turbulent bed weight space velocity is 0.1- 100hr ^-1 , the reaction pressure is 0.1-0.4MPa. The reacted catalyst enters the stripping section 318 of the auxiliary fluidized reactor 313, and is in countercurrent contact with the stripping steam 319 introduced from the bottom of the stripping section 318 to strip the oil and gas entrained by the catalyst. The stripped catalyst enters the regenerator 303 through the inclined pipe 312 . The reacted oil gas enters the settling section 315 of the auxiliary fluidized reactor 313, and then enters the top cyclone separator 321 to be separated from the catalyst carried. After the oil gas 322 completely separated from the catalyst leaves the auxiliary fluidized reactor, it enters the oil-gas separation system.

3. The present invention also includes setting up a separate C4 hydrocarbon catalytic conversion reactor to convert C4 hydrocarbons, and then introducing the cracking catalyst after cooling into the catalytic gasoline reforming auxiliary reactor to carry out the reforming and reducing olefin reaction of catalytic gasoline, then it can Obtain the invention flow chart of Fig. 4. The brief description is as follows: a special C4 hydrocarbon catalytic conversion reactor 413 and an auxiliary riser reactor 415 for catalytic gasoline upgrading and olefin reduction are set up next to the regenerator 403 of the original catalytic cracking unit. 403 enters the bottom of the reactor 413 and mixes with C4 hydrocarbons 412 with a preheating temperature of 40-300°C. After the reaction temperature is 400-650°C, the weight ratio of catalyst to C4 hydrocarbons is 2-100, and the catalyst activity is 53- 70, the reaction time is 2.0-100.0s or the weight space velocity is 0.1-100hr ^-1 , and the reaction pressure is 0.1-0.4MPa to carry out contact, mixing and catalytic conversion reaction to increase the production of aromatics and ethylene and propylene. The reaction oil gas enters the settler 419 of the auxiliary riser reactor through the pipeline 423, and the catalyst enters the bottom of the auxiliary riser reactor 415 through the inclined pipe 414, mixes with the pre-lifting steam 416, and then lifts upward to the catalytic cracking gasoline fraction 417 at the reaction temperature 350-600°C, gasoline feedstock preheating temperature 40-200°C, catalyst oil weight ratio 2-20, catalyst activity 55-65, reaction time 2.0-20.0s, reaction pressure 0.1-0.4MPa Contact, gasification, mixing and reaction, the reaction oil gas, water vapor and catalyst pass through the riser reactor 415, and at its outlet, the modified oil gas and catalyst are separated by the high-efficiency gas-solid rapid separation device 418, and the catalyst enters the settler 419 and steam The stripping section 420 enters the regenerator 403 through the inclined pipe 422 after being stripped by the stripping steam 421 . After the reaction oil gas 424 leaves the settler 419, it enters the oil gas separation system.

4. The form of the special C4 hydrocarbon catalytic conversion reactor in Fig. 4 is changed to the form of a riser plus a turbulent bed, thus the inventive process of Fig. 5 can be obtained. The brief description is as follows: a special C4 hydrocarbon catalytic conversion reactor 513 and an auxiliary reactor 515 for catalytic gasoline upgrading and olefin reduction are set up next to the regenerator 503 of the original catalytic cracking unit. The regenerated high-temperature catalyst first enters from the regenerator 503 through an inclined pipe 511 The bottom of the reactor 513 is mixed with C4 hydrocarbons 512 at a preheating temperature of 40-300°C, the reaction temperature is 400-650°C, the weight ratio of catalyst to C4 hydrocarbons is 2-100, and the catalyst activity is 53-70, The reaction time is 2.0-100.0s or the weight space velocity is 0.1-100hr ^-1 , and the reaction pressure is 0.1-0.4MPa to carry out contact, mixing and catalytic conversion reaction to increase the production of aromatics and ethylene and propylene. The reaction oil gas enters the settler 524 of the auxiliary riser reactor through the pipeline 522, and the catalyst enters the bottom of the auxiliary fluidized reactor 515 through the inclined pipe 514, mixes with the pre-lifting steam 516, and then lifts up to the catalytic cracker containing atomized steam. The reaction temperature of gasoline fraction 517 is 350-600°C, the preheating temperature of gasoline raw material is 40-200°C, the weight ratio of catalyst to oil is 2-20, the catalyst activity is 55-65, and the reaction time of riser section is 1.0-20.0s, The weight space velocity of the fluidized bed is 1-1000h ^-1 , and the reaction pressure is 0.1-0.4MPa to carry out contact, gasification, mixing and reaction, and the reaction oil gas, water vapor and catalyst pass through the riser reactor 51 5 to its outlet The upgraded oil gas and the catalyst are separated by the high-efficiency gas-solid rapid separation device 519, and the catalyst enters the settler 524 and the stripping section 518, and enters the regenerator 503 through the inclined pipe 521 after being stripped by the stripping steam 520. After the reaction oil gas 523 leaves the settler 524, it enters the oil gas separation system.

5. The special C4 hydrocarbon catalytic conversion reactor in Fig. 4 is changed into a turbulent bed form, thus the invention process of Fig. 6 can be obtained, which is briefly described as follows: a special C4 hydrocarbon is set up next to the original catalytic cracking unit regenerator 603 Catalytic conversion reactor 613 and auxiliary fluidized reactor 615 for catalytic gasoline modification and olefin reduction. The regenerated high-temperature catalyst first enters the bottom of reactor 613 from regenerator 603 through inclined pipe 611, and the preheating temperature is 40-300°C After mixing the C4 hydrocarbons 612, the reaction temperature is 400-650°C, the weight ratio of the catalyst to the C4 hydrocarbons is 2-100, the catalyst activity is 53-70, the reaction time is 2.0-100.0s or the weight space velocity is 0.1-100hr ^-1 , the reaction pressure is 0.1-0.4MPa to carry out contact, mixing and catalytic conversion reaction to increase the production of aromatics and ethylene and propylene. The reaction oil gas enters the settling section 625 of the auxiliary fluidized reactor through the pipeline 622, and the catalyst enters the bottom of the auxiliary fluidized reactor 615 through the inclined pipe 614, mixes with the pre-lifting steam 616, and then lifts to the auxiliary fluidized reactor 615 A reaction bed 620 is formed inside, the upper nozzle of the catalyst riser is at the top of the reaction bed 620, and the catalytically cracked gasoline fraction 617 containing atomized steam enters the lower part of the auxiliary fluidized reactor bed 620 through the nozzle, and is connected with the bed 620 The catalysts in the catalyst are contacted, gasified, mixed and reacted. In the reaction bed 620 of the auxiliary fluidized reactor 615, the reaction temperature is maintained at 350-600°C, the raw material preheating temperature is 40-300°C, the catalyst activity is 50-70, and the turbulent bed weight space velocity is 1- 1000hr ^-1 , the reaction pressure is 0.1-0.4MPa. The reacted catalyst enters the stripping section 618 of the auxiliary fluidized reactor 615, and is in countercurrent contact with the stripping steam 619 introduced from the bottom of the stripping section 618 to strip the oil and gas entrained by the catalyst. The stripped catalyst enters the regenerator 603 through the inclined pipe 621 . The reacted oil gas enters the settling section 625 of the auxiliary fluidized reactor 615, and then enters the top cyclone separator 623 to be separated from the carried catalyst, and the oil gas 624 completely separated from the catalyst leaves the auxiliary fluidized reactor and enters the oil-gas separation system.

If the present invention is realized in the riser pre-lift section of conventional heavy oil catalytic cracking unit, two situations will be included:

1. The inventive process shown in FIG. 7 is briefly described as follows: C4 hydrocarbons 711 with a preheating temperature of 40-300° C. enter the pre-lift section of the riser reactor 702 from the bottom and the steam 704 lifts the gas from the regenerator 703 After mixing the high-temperature regenerant 705, the reaction temperature is 400-650°C, the weight ratio of catalyst to C4 hydrocarbons is 2-100, the catalyst activity is 53-70, the reaction time is 2.0-100.0s or the weight space velocity is 0.1- 100hr ^-1 , and the reaction pressure is 0.1-0.4MPa to carry out contact, mixing and catalytic conversion reactions to increase the production of aromatics, ethylene and propylene. The reaction product and the catalyst are lifted together and mixed with the heavy oil raw material 701 containing atomized steam. The reaction temperature is 460-530°C, the preheating temperature of the heavy oil raw material is 160-250°C, the weight ratio of the catalyst to oil is 5-8, and the catalyst activity is 50 -70, the reaction time is 2.5-3.0s, and the reaction pressure is 0.1-0.4MPa to carry out contact, gasification, mixing and reaction, oil gas, water vapor and catalyst pass through the riser reactor 702 to the outlet of the riser reactor 702 The reaction oil gas 710 and the catalyst are separated by the high-efficiency gas-solid rapid separation device 706 and the top spin of the settler 707. The catalyst enters the stripping section 709 through the settler 708, and enters the regenerator 703 after being stripped. The reaction oil gas 710 leaves the settler 708 and enters the fractionation system for separation of rich gas, gasoline, diesel oil, recycled oil, and oil slurry.

2. The inventive process shown in Fig. 8 is realized in the pre-lifting section modified by enlarging the inner diameter, and the brief description is as follows: C4 hydrocarbons 811 with a preheating temperature of 40-300°C first enter the main riser reactor 802 from the bottom At the bottom of the enlarged section 812 at the bottom, the reaction temperature with the high-temperature regenerant 805 from the regenerator 803 is 400-650°C, the weight ratio of the catalyst to C4 hydrocarbons is 2-100, the catalyst activity is 53-70, and the reaction time is 2.0- 100.0s or the weight space velocity is 0.1-100hr ^-1 , and the reaction pressure is 0.1-0.4MPa to carry out contact, mixing and catalytic conversion reaction to increase the production of aromatics and ethylene and propylene. Thereafter, the reaction product and the catalyst flow upward together and enter the main riser reactor 802 to mix with the heavy oil feedstock 801 containing atomized steam. The reaction temperature is 460-530°C, and the preheating temperature of the heavy oil feedstock is 160-250°C. The weight ratio of the catalyst to oil is 5-8, the catalyst activity is 50-70, the reaction time is 2.5-3.0s, and the reaction pressure is 0.1-0.4MPa to carry out contact, gasification, mixing and reaction, oil gas, water vapor and the catalyst pass together Riser reactor 802, to the outlet of riser reactor 802, the reaction oil gas 810 and the catalyst are separated by the high-efficiency gas-solid rapid separation device 806 and the settler top rotation 807, and the catalyst enters the stripping section 809 through the settler 808, and after stripping Enter regenerator 803. The reaction oil gas 810 leaves the settler 808 and enters the fractionation system for separation of rich gas, naphtha, diesel oil, recycled oil, and oil slurry.

If the present invention reacts C4 hydrocarbons in the heavy oil catalytic cracking reactor and the auxiliary fluidized reactor for catalytic gasoline modification and reduction of olefins simultaneously, it also includes the following reaction forms:

1. If it is implemented simultaneously in the pre-lift section of the conventional heavy oil catalytic cracking riser reactor and the pre-lift section of the catalytic gasoline modified olefin-reducing auxiliary reactor, the inventive process of Fig. 9 can be obtained, and details can be seen in Fig. 7 and Fig. 1 describe;

2. The form of the auxiliary reactor in Fig. 9 is changed to a riser and a turbulent bed form, and the invention process of Fig. 10 can be obtained, and the description to Fig. 7 and Fig. 2 can be seen in detail;

3. The form of the auxiliary reactor in Fig. 9 is changed to the form of a turbulent bed, and the invention process of Fig. 11 can be obtained, and the description to Fig. 7 and Fig. 3 can be seen in detail;

4. If the catalytic upgrading of C4 hydrocarbons is carried out in the pre-lifting section of the riser of the conventional heavy oil catalytic cracking unit and the separately established C4 hydrocarbon catalytic conversion reactor, then the temperature of the separately established C4 hydrocarbon catalytic conversion reactor is cooled The final catalyst is introduced into the auxiliary reactor for catalytic gasoline modification and olefin reduction for reaction, and the invention flow chart in Fig. 12 can be obtained, and the description of Fig. 7 and Fig. 4 can be seen in detail;

5. The form of the auxiliary reactor in Figure 12 is changed to a riser plus a turbulent bed form, and the invention process of Figure 13 can be obtained, as can be seen in the description of Figure 7 and Figure 5 in detail;

6. Change the form of auxiliary reactor in Fig. 12 to the form of turbulent bed, and the invention process of Fig. 14 can be obtained, and the description to Fig. 7 and Fig. 6 can be seen in detail;

7. If the catalytic upgrading of C4 hydrocarbons is simultaneously realized in the pre-lifting section of the riser of the conventional heavy oil catalytic cracking unit and the pre-lifting section of the auxiliary reactor for catalytic gasoline upgrading and olefin reduction through the expansion of the internal diameter, the inventive process shown in Figure 15 can be obtained , see the description of Figure 8 and Figure 1 for details;

8. The form of the auxiliary reactor in Fig. 15 is changed to a riser plus a turbulent bed form, and the invention process of Fig. 16 can be obtained, and the description to Fig. 8 and Fig. 2 can be seen in detail;

9. The form of the auxiliary reactor in Figure 15 is changed to the form of a turbulent bed, and the invention process of Figure 17 can be obtained, as can be seen in the description of Figure 8 and Figure 3 in detail;

10. If the catalytic upgrading of C4 hydrocarbons is realized in the pre-lifting section of the riser of the conventional heavy oil catalytic cracking unit modified with enlarged inner diameter and in the separately established C4 hydrocarbon catalytic conversion reactor, then the C4 hydrocarbons that have passed through the separately established The catalyst after cooling down in the similar catalytic conversion reactor is introduced into the auxiliary riser reactor for catalytic gasoline modification and olefin reduction for reaction, and the invention flow chart in Fig. 18 can be obtained, and the description of Fig. 8 and Fig. 4 can be seen in detail;

11. The form of the auxiliary reactor in Fig. 18 is changed to the form of a riser plus a turbulent bed, and the invention process of Fig. 19 can be obtained, and the description to Fig. 8 and Fig. 5 can be seen in detail;

12. The form of the auxiliary reactor in Figure 18 is changed to the form of a turbulent bed, and the invention process of Figure 20 can be obtained, and the description of Figure 8 and Figure 6 can be seen in detail.

The catalyst used in the present invention can be any catalyst suitable for the catalytic cracking process, that is, the catalytic cracking gasoline upgrading reaction is realized by the catalyst of the original heavy oil catalytic cracking unit. For example, an amorphous silica-alumina catalyst or a molecular sieve catalyst, wherein the active component of the molecular sieve catalyst is selected from Y-type or HY-type zeolite containing or not containing rare earth or phosphorus, ultrastable Y-type zeolite containing or not containing rare earth or phosphorus, One or more of ZSM-5 series zeolite or silica zeolite with five-membered ring structure, beta zeolite and ferrierite.

Finally, it should be noted that the above embodiments are only used to illustrate and not limit the technical solutions of the present invention, although the present invention has been described in detail with reference to the above embodiments, those of ordinary skill in the art should understand that: the present invention can still be modified Or an equivalent replacement, any modification or partial replacement without departing from the spirit and scope of the present invention shall fall within the scope of the claims of the present invention.

Claims (9)

1. An effective process for the catalytic conversion of C4 hydrocarbons, characterized in that: the pre-lift section of the catalytic gasoline reforming auxiliary reactor or the pre-lift section of the catalytic cracking of heavy oil is used as the C4 hydrocarbon catalytic conversion reactor, or A separate C4 hydrocarbon catalytic conversion reactor is set up before the catalytic gasoline upgrading auxiliary reactor. The regenerated high-temperature catalyst enters the bottom of the C4 hydrocarbon catalytic conversion reactor from the regenerator through an inclined pipe and the preheating temperature is 40-300 °C After the C4 hydrocarbons are mixed, the reaction temperature is 400-650°C, the weight ratio of catalyst to C4 hydrocarbons is 2-100, the catalyst activity is 53-70, the reaction time is 2.0-100.0s or the weight space velocity is 0.1-100hr ^{- 1.} Carry out contact, mixing and catalytic conversion reactions at a reaction pressure of 0.1-0.4 MPa to increase the production of aromatics and ethylene and propylene. 2. The process for catalytic conversion of C4 hydrocarbons according to claim 1, characterized in that: when the C4 hydrocarbons enter the catalytic conversion reactor of C4 hydrocarbons from the bottom at a preheating temperature of 40-300°C, It is the riser pre-lift section of the catalytic gasoline upgrading auxiliary reactor; or a special C4 hydrocarbon catalytic conversion reactor separately installed in front of the catalytic gasoline upgrading auxiliary reactor; it can also be the heavy oil catalytic cracking riser pre-lift section, Wherein: it can be the pre-lifting section of the original riser, or a reaction zone with an enlarged inner diameter is added at the pre-lifting section. 3. The process for catalytic conversion of C4 hydrocarbons according to claim 1, characterized in that: the pre-lifting section of the catalytic gasoline reforming auxiliary reactor is used as a catalytic conversion reactor for C4 hydrocarbons, and the reaction product and the catalyst are lifted together With the catalytic gasoline fraction, the reaction temperature is 350-600°C, the gasoline raw material preheating temperature is 40-200°C, the catalyst oil weight ratio is 2-20, the catalyst activity is 55-65, the reaction time is 2.0-20.0s, and the reaction pressure Contact, gasification, mixing and reaction are carried out at 0.1-0.4MPa; the reacted oil gas and catalyst pass through the catalytic gasoline upgrading auxiliary reactor, and at its outlet, the upgraded oil gas and catalyst are separated by a high-efficiency gas-solid rapid separation device, and the catalyst enters The settler and the stripping section enter the regenerator through the inclined tube after being stripped by the stripping steam; after the reaction oil gas leaves the settler, it enters the oil-gas separation system. 4. The process for catalytic conversion of C4 hydrocarbons according to claim 1 or 3, characterized in that: the catalytic gasoline upgrading auxiliary reactor is in the form of an auxiliary riser reactor, and is changed to a riser plus a turbulent bed form or turbulent bed form. 5. The process method of catalytic conversion of C4 hydrocarbons according to claim 1, characterized in that: the catalytic conversion of C4 hydrocarbons is carried out with a special C4 hydrocarbon catalytic conversion reactor separately arranged in front of the catalytic gasoline reforming auxiliary reactor Finally, the cooled cracking catalyst is introduced into the catalytic gasoline reforming auxiliary reactor for catalytic gasoline reforming and olefin reduction reaction, and the reaction product is directly introduced into the catalytic gasoline reforming auxiliary reactor settler. 6. The process for catalytic conversion of C4 hydrocarbons according to claim 1, characterized in that: the pre-lift section of the heavy oil catalytic cracking riser or a reaction zone with enlarged inner diameter is added at the pre-lift section as the catalytic conversion of C4 hydrocarbons In the reactor, the reaction product and the catalyst are lifted together and mixed with the heavy oil raw material containing atomized steam. The activity is 50-70, the reaction time is 2.5-3.0s, and the reaction pressure is 0.1-0.4MPa to carry out contact, gasification, mixing and reaction. Oil gas, water vapor and catalyst pass through the main riser reactor together to react in the riser At the outlet of the reactor, the high-efficiency gas-solid rapid separation device and the top rotation of the settler separate the reaction oil gas from the catalyst. The catalyst enters the stripping section through the settler, and enters the regenerator after stripping; the reaction oil gas leaves the settler and enters the fractionation system for separation. 7. The process for catalytic conversion of C4 hydrocarbons according to claim 1, characterized in that: both the pre-lift section of the catalytic gasoline reforming auxiliary reactor and the pre-lift section of heavy oil catalytic cracking can be used as C4 hydrocarbon catalytic converters at the same time. The conversion reactor is used for catalytic conversion reaction of C4 hydrocarbons to increase the production of aromatics, ethylene and propylene. 8. The process method for catalytic conversion of C4 hydrocarbons according to claim 1, characterized in that: the pre-lifting section of heavy oil catalytic cracking and the catalytic conversion of C4 hydrocarbons separately set up before the catalytic gasoline upgrading auxiliary reactor can be simultaneously The reactors are all used as C4 hydrocarbon catalytic conversion reactors to perform catalytic conversion reaction on C4 hydrocarbons to increase the production of aromatics, ethylene and propylene. 9. The process for catalytic conversion of C4 hydrocarbons according to claim 1, characterized in that the catalyst used may be an amorphous silica-alumina catalyst or a molecular sieve catalyst.

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