CN112745903A

CN112745903A - Process and apparatus for catalytic conversion of heavy petroleum hydrocarbon feedstocks

Info

Publication number: CN112745903A
Application number: CN201911053150.8A
Authority: CN
Inventors: 成晓洁; 谢朝钢; 朱根权; 杨超; 沙有鑫
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2019-10-31
Filing date: 2019-10-31
Publication date: 2021-05-04
Anticipated expiration: 2039-10-31
Also published as: CN112745903B

Abstract

The invention relates to the field of hydrocarbon oil processing, and discloses a method and a device for catalytic conversion of a heavy petroleum hydrocarbon raw material, wherein the method comprises the following steps: (1) contacting a raw material I with a catalyst I in a first reactor; (2) introducing the stream in the first reactor into a third reactor to perform a third catalytic cracking reaction with the stream containing the catalyst II entering from the second reactor; (3) separating the material flow obtained after the reaction in a settler; (4) introducing the spent catalyst into a regenerator for regeneration, dividing the regenerated catalyst into a catalyst I and a catalyst II for circulation, and introducing the spent catalyst which is used as the catalyst II for circulation into a second reactor after being led out from the regenerator or after not undergoing heat exchange. The method provided by the invention can realize flexible modulation of the product structure and has high process flexibility.

Description

Process and apparatus for catalytic conversion of heavy petroleum hydrocarbon feedstocks

Technical Field

The invention relates to the field of hydrocarbon oil processing, in particular to a method for catalytically converting a heavy petroleum hydrocarbon raw material and a device for catalytically converting the heavy petroleum hydrocarbon raw material.

Background

The low-carbon olefin is an important chemical raw material, the dominant technology for producing ethylene and propylene worldwide is steam cracking at present, and about more than 95 percent of ethylene and more than 60 percent of propylene are obtained by the technology.

Worldwide, naphtha accounts for 48% of cracking raw materials, ethane accounts for 33%, propane accounts for 8%, butane accounts for about 5%, oil gas accounts for 4%, and the rest accounts for about 2%. In the steam cracking process, because no catalyst exists, the cracking of hydrocarbons needs more severe operating conditions, so that the production and device construction cost is higher, crude oil is gradually transformed, light hydrocarbon raw materials are increasingly lacking, and the development of a technical route for producing low-carbon olefins by using heavy oil as a raw material becomes a poor choice for producing low-carbon olefins.

Therefore, the technological route for producing light olefins from heavy oil, as represented by catalytic cracking, is rapidly developed and widely welcomed.

The catalytic cracking process is described in detail by the technologies of CN1031834A, US4980053A, CN1102431A and the like. The catalytic cracking process adopts a reactor type of connecting a riser or a descending conveyor line reactor and a fluidized bed or a moving bed reactor in series, and uses a solid acid catalyst containing zeolite with an MFI structure, such as ZSM-5, ZRP and the like, rare earth-containing pentasil zeolite and phosphorus-containing pentasil zeolite. The optimal reaction conditions are as follows: the reaction temperature is 500-600 ℃, the reaction time is 1-6 s, and the solvent-oil ratio is 6-15: 1. The yields of propylene and butylene amounted to about 35 wt.%, and the gasoline yield was about 25 wt.%.

Based on the national conditions of China, gasoline is still the main traffic fuel and the main product of a catalytic cracking unit in a long period of time in the future. With increasingly strict requirements on the quality of gasoline products by the environment, the quality standard of gasoline is continuously upgraded, China runs a development road for over fifty years in developed countries in more than ten years, and according to the national six-gasoline standard, the olefin content in the gasoline component is below 15 wt%, and the sulfur content is below 10 ppm.

Along with the continuous change of market quotations, the requirements of oil refining production enterprises on product distribution at different periods are changed, the newly-built device is difficult, heavy and large in investment, and if the processing mode of the heavy oil catalytic conversion device can be flexibly adjusted according to the change of market requirements, the method has great economic significance in adapting to the production of different target products.

Disclosure of Invention

The invention aims to realize flexible switching between a mode of producing more light olefins and a mode of producing more gasoline.

To achieve the above object, a first aspect of the present invention provides a process for the catalytic conversion of a heavy petroleum hydrocarbon feedstock, the process being carried out in an apparatus comprising a first reactor, a second reactor, a third reactor, a settler and a regenerator, the process comprising:

(1) contacting a heavy petroleum hydrocarbon feedstock I with a regenerated catalytic cracking catalyst I in the first reactor to perform a first catalytic cracking reaction;

(2) introducing the stream in the first reactor into the third reactor in communication with the first reactor outlet for a third catalytic cracking reaction with a stream containing regenerated catalytic cracking catalyst II entering the third reactor from the second reactor;

(3) separating the material flow obtained after the third catalytic cracking reaction in the settler to obtain reaction oil gas and spent catalyst;

(4) introducing the spent catalyst into the regenerator for regeneration to obtain regenerated catalyst, and circulating at least part of the regenerated catalyst as the regenerated catalytic cracking catalyst I and the regenerated catalytic cracking catalyst II,

wherein the second reactor is a conveying pipe or a reactor for carrying out catalytic cracking reaction; and the spent catalyst which is used as the regenerated catalytic cracking catalyst II for circulation is led out from the regenerator and then led into the second reactor after or without heat exchange.

In a second aspect, the present invention provides an apparatus for the catalytic conversion of a heavy petroleum hydrocarbon feedstock, the apparatus comprising a first reactor, a second reactor, a third reactor, a settler, a gas-solid separator, a stripper, and a regenerator,

the first reactor is coaxial with and in communication with the third reactor, the settler with the gas-solid separator therein, the stripper;

the settler is located above the third reactor; the stripper is positioned below the third reactor; one end opening of the first reactor is positioned in the third reactor;

the second reactor is positioned outside the stripper, one end of the second reactor penetrates through the outer wall of the settler and extends into the interior of the settler, and at least one opening of the second reactor is positioned at the upper part of the third reactor;

the stripper is in communication with the regenerator via a line, and the regenerator is also in communication with the first and second reactors via lines, respectively; and a pipeline for communicating the regenerator with the second reactor is provided with or externally connected with heat exchange equipment.

The method provided by the invention can realize flexible modulation of the product structure and has high process flexibility.

Compared with the existing hydrocarbon catalytic conversion method, the hydrocarbon catalytic conversion method provided by the invention has high operation flexibility, can flexibly change the operation mode according to market conditions, realizes different production purposes of producing more low-carbon olefins and more gasoline, and the like, and can reach the level of the prior art.

The device provided by the invention has the advantages of simple structure, low modification cost, high process flexibility, high catalyst utilization efficiency, reduced energy consumption and correspondingly lower environmental load.

Drawings

FIG. 1 is a schematic diagram of an apparatus for the catalytic conversion of a heavy petroleum hydrocarbon feedstock in accordance with a preferred embodiment of the present invention;

FIG. 2 is a schematic diagram of an apparatus for the catalytic conversion of heavy petroleum hydrocarbon feedstocks, which is another preferred embodiment of the present invention.

Description of the reference numerals

1. First reactor

2. Second reactor

3. Third reactor

4. Settling vessel

41. Gas-solid separator

5. Steam stripping device

6. Regenerator

7. Heat exchange equipment

12. First regeneration inclined pipe

22. Second regeneration inclined tube

Detailed Description

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

In the context of the present invention, unless otherwise specified, the term "lower olefins" means C2-C4 olefins and "gasoline" means C5-C12 components.

As previously mentioned, a first aspect of the present invention provides a process for the catalytic conversion of a heavy petroleum hydrocarbon feedstock, the process being carried out in an apparatus comprising a first reactor, a second reactor, a third reactor, a settler and a regenerator, the process comprising:

According to a preferred embodiment, the method is a method for catalyzing the heavy petroleum hydrocarbon feedstock to produce higher yields of lower olefins, and the second reactor is a reactor for performing catalytic cracking reactions.

In the aforementioned preferred embodiment, it is preferred that the method further comprises: and carrying out a second catalytic cracking reaction on the light petroleum hydrocarbon raw material I and the regenerated catalytic cracking catalyst II in the second reactor.

According to another preferred embodiment, the method is a method for catalyzing the heavy petroleum hydrocarbon feedstock to produce higher yields of lower olefins, and the second reactor is a transport pipe.

More preferably, the method is a method for catalyzing the heavy petroleum hydrocarbon raw material to produce more low-carbon olefins, the reaction temperature of the first reactor is 480-620 ℃, and the reaction temperature of the third reactor is 500-650 ℃.

Preferably, the method is a method for catalyzing the heavy petroleum hydrocarbon raw material to produce more light olefins, and the outlet temperature of the second reactor (or the conveyor) is 550-750 ℃. More preferably, when the second catalytic cracking reaction is carried out in the second reactor, the reaction temperature of the second reactor is adjusted within the range of 500-680 ℃ according to the cracking performance of the light petroleum hydrocarbon raw material I, and the catalyst-oil ratio is within the range of 5-30: 1. More preferably, the conditions of the second catalytic cracking reaction include: the reaction temperature is 580-660 ℃, and the catalyst-oil ratio is 10-25: 1. Preferably, the injection of gas at different locations in the second reactor, including but not limited to steam, catalytic cracking dry gas, hydrogen, C1-C4 hydrocarbons, and mixtures of two or more of the foregoing containing oxygen, serves to fluidize the catalyst, adjust the linear velocity of the catalyst-oil mixture, and reduce the partial pressure of the hydrocarbons. The ratio of the injection amount of the gas to the amount of the light petroleum hydrocarbon raw material I is 0.1-1: 1. according to a preferred embodiment, the process is a process for the production of gasoline in excess of the heavy petroleum hydrocarbon feedstock, and the second reactor is a transfer line.

Preferably, the method is a method for catalyzing the heavy petroleum hydrocarbon raw material to produce gasoline in high yield, wherein the reaction temperature of the first reactor is 480-560 ℃, the temperature of the outlet of the second reactor is 400-540 ℃, and the reaction temperature of the third reactor is 450-550 ℃.

According to the process of the present invention, preferably, the operating conditions in the first reactor comprise: the agent-to-oil ratio (the weight ratio of the regenerated catalytic cracking catalyst I introduced into the first reactor to the heavy petroleum hydrocarbon feedstock I) is from 4 to 20: 1; a water to oil ratio (weight ratio of steam to heavy petroleum hydrocarbon feedstock I) of 0.1 to 0.5: 1; the reaction time is 0.1-5s, more preferably 1-5s, and the absolute pressure of the reaction zone (generally the pressure of the settler) is 0.15-0.50 MPa, preferably 0.20-0.37 MPa.

According to the process of the present invention, preferably, the operating conditions in the second reactor comprise: the weight ratio of the catalyst in the second reactor to the catalyst in the first reactor is 0.1-1: 1.

according to the process of the present invention, preferably, the operating conditions in the first reactor comprise: the weight hourly space velocity is 0.2-30h^-1More preferably 0.5 to 20 hours^-1。

The first reactor can be a riser reactor, a descending conveyor line reactor or a composite reactor formed by connecting a plurality of reactors in series and/or in parallel, and the reactor can be divided into two or more reaction zones according to requirements. The first reactor is preferably a riser reactor, and the riser reactor is one or more of an equal-diameter riser reactor, an equal-linear-speed riser reactor and a variable-diameter riser reactor.

The second reactor may be a riser reactor, a down-flow line reactor or a combined reactor consisting of a plurality of the above reactors connected in series and/or in parallel, preferably a riser reactor. When the operation mode of producing more light olefins is adopted, the light petroleum hydrocarbon raw material I can enter the second reactor to perform catalytic reaction. The second reactor functions only as a catalyst transporter when a productive gasoline mode of operation is assumed.

The third reactor is preferably a fluidized bed reactor, and can be one or a plurality of fluidized bed reactors connected in parallel or in series; the fluidized bed reactor is selected from one or more of a fixed fluidized bed reactor, a bulk fluidized bed reactor, a bubbling bed reactor, a turbulent bed reactor, a fast bed reactor, a conveying bed reactor and a dense-phase fluidized bed reactor.

Particularly preferably, the first reactor and the second reactor are riser reactors and the third reactor is a fluidized bed reactor.

According to a preferred embodiment, the method is a method for catalyzing the heavy petroleum hydrocarbon raw material to produce gasoline in a high yield, and the spent catalyst which is circulated as the regenerated catalytic cracking catalyst II is led out from the regenerator, then is introduced into the second reactor after being subjected to heat exchange and temperature reduction in a heat remover.

Preferably, the heat collector is an external heat exchanger.

Preferably, the heavy petroleum hydrocarbon feedstock I is a grease and/or a heavy hydrocarbon selected from at least one of diesel, hydrogenated tail oil, vacuum gas oil, crude oil, residual oil, coal liquefaction oil, oil sand oil and shale oil.

The oil and fat can be one or more selected from animal and vegetable oil and fat.

Preferably, the light petroleum hydrocarbon feedstock I is selected from at least one of cracked light gasoline and cracked C4 hydrocarbon components. More preferably, the cracked light gasoline and/or the cracked C4 hydrocarbon components are subjected to hydrogenation reaction to remove dienes and alkynes, and then are introduced into the second reactor.

In the method of the present invention, there is no particular requirement on the specific type of the regenerated catalytic cracking catalyst, and the regenerated catalytic cracking catalyst may be a catalyst that is conventionally used in the art to catalyze the heavy petroleum hydrocarbon feedstock to produce a higher yield of lower olefins or a higher yield of lower olefins, and may be, for example, a cracking catalyst containing shape-selective zeolite.

More specifically, in the process of the invention, different corresponding catalysts can be used in different operating modes. When a mode of producing more light olefins is adopted, the active component of the regenerated catalytic cracking catalyst is selected from quinary ring high-silicon zeolite containing rare earth and phosphorus and Y-type zeolite containing or not containing rare earth and the carrier is selected from alumina, aluminum silicate, natural clay and alumina by taking the total weight of the regenerated catalytic cracking catalyst as a reference. When the productive gasoline operation mode is adopted, the active components of the regenerated catalytic cracking catalyst are selected from one, two or three of Y or HY type zeolite containing or not containing rare earth, ultrastable Y type zeolite containing or not containing rare earth, ZSM-5 series zeolite or high-silicon zeolite with five-membered ring structure, and amorphous silicon-aluminum catalyst.

One preferred embodiment of the process for the catalytic conversion of a heavy petroleum hydrocarbon feedstock of the present invention is provided below, which comprises:

(1) preheating a heavy petroleum hydrocarbon raw material I, and then contacting the heavy petroleum hydrocarbon raw material I with a hot regenerated catalytic cracking catalyst I at the lower part of a first reactor to perform a first catalytic cracking reaction;

(3) separating the material flow obtained after the third catalytic cracking reaction in the settler to obtain reaction oil gas (the reaction oil gas is introduced into a fractionation device for fractionation) and spent catalyst;

(4) introducing the spent catalyst into a settler, then feeding the spent catalyst into a stripper, then conveying the spent catalyst into a regenerator for regeneration to obtain a regenerated catalyst, and circulating at least part of the regenerated catalyst as a regenerated catalytic cracking catalyst I and a regenerated catalytic cracking catalyst II,

the regenerated catalyst serving as the regenerated catalytic cracking catalyst I directly enters the lower part of the first reactor, and the regenerated catalyst serving as the regenerated catalytic cracking catalyst II flows through the catalyst heat exchange device, so that the temperature of the regenerated catalyst can be adjusted.

When the operation mode of producing more light olefins is adopted, the regenerated catalyst serving as the regenerated catalytic cracking catalyst II does not exchange heat and directly enters the second reactor and is conveyed to the third reactor.

When the operation mode of producing gasoline in high yield is adopted, the regenerated catalyst used as the regenerated catalytic cracking catalyst II is subjected to heat exchange to obtain a low-temperature regenerated catalyst, and then the low-temperature regenerated catalyst is conveyed to a third reactor through the second reactor.

The heat exchange of the spent catalyst which is circulated as the regenerated catalytic cracking catalyst II in the invention can be realized by a heat exchanger, an external heat exchanger or a method of injecting a cooling medium after the spent catalyst is led out from the regenerator and then is introduced into the second reactor after heat exchange, and the heat exchanger can be at least one selected from a jacketed heat exchanger, an immersed heat exchanger, a shell-and-tube heat exchanger, a mixed heat exchanger and the like, or can be the combination of two or more heat exchangers. The heat-extracting medium may be selected from, but not limited to, one of water, nitrogen, dry gas, and the like. The external heat collector can adopt the existing external heat collector of the device or a newly-built external heat collector, and the heated catalyst does not return to the regenerator completely, but has a part flowing into a regeneration inclined pipe connected with the bottom of the external heat collector. When heat is extracted by injection of a cooling medium, the cooling medium may be selected from, but not limited to, water, catalytic cracking dry gas, hydrogen, and the like.

The heat extraction amount of the heat exchange area is set according to the operation mode of the device. When the reactor is operated in a mode of producing more light olefins, the heat exchange area can choose not to take or take less heat, so that the regenerated catalyst enters the second reactor while keeping high temperature, and the temperature of the part of the regenerated catalyst is 630-750 ℃. When the gasoline productive mode is used for operation, the heat exchange area can increase the heat quantity, so that the temperature of the part of regenerated catalyst is greatly reduced and then is conveyed to the downstream through the second reactor, and under the condition, the temperature of the part of regenerated catalyst is 400-550 ℃.

As previously mentioned, a second aspect of the present invention provides an apparatus for the catalytic conversion of a heavy petroleum hydrocarbon feedstock comprising a first reactor, a second reactor, a third reactor, a settler, a gas-solid separator, a stripper, and a regenerator,

Preferably, in the second aspect of the present invention, the first reactor and the second reactor are riser reactors, and the third reactor is a fluidized bed reactor.

The following provides a preferred embodiment of the apparatus for catalytic conversion of a heavy petroleum hydrocarbon feedstock of the present invention comprising a first reactor, a second reactor, a third reactor, a settler, a gas-solid separator, a stripper, and a regenerator,

the first reactor and the second reactor are both riser reactors, the third reactor is a fluidized bed reactor,

the stripper is in communication with the regenerator via a line, and the regenerator is also in communication with the first and second reactors via first and second regeneration ramps, respectively; and the second regeneration inclined tube is provided with or externally connected with heat exchange equipment.

Preferred embodiments of the apparatus and method of the present invention will be described below with reference to the accompanying drawings.

In FIG. 1, the apparatus comprises a first reactor 1, a second reactor 2, a third reactor 3, a settler 4, a gas-solid separator 41, a stripper 5 and a regenerator 6,

the first reactor 1 and the second reactor 2 are both riser reactors, the third reactor 3 is a fluidized bed reactor,

the first reactor 1 is coaxial and in communication with the third reactor 3, the settler 4 with the gas-solid separator 41 therein, the stripper 5;

the settler 4 is located above the third reactor 3; the stripper 5 is located below the third reactor 3; one end of the first reactor 1 is opened and positioned in the third reactor 3;

the second reactor 2 is positioned outside the stripper 5, one end of the second reactor 2 passes through the outer wall of the settler 4 and extends into the interior of the settler 4, and at least one opening of the second reactor 2 is positioned at the upper part of the third reactor 3;

the stripper 5 is in communication with the regenerator 6 by means of a line, and the regenerator 6 is also in communication with the first and second reactors 1 and 2 by means of first and second regeneration ramps 12 and 22, respectively; the second regeneration inclined tube 22 is provided with a heat exchange device 7.

The hot regenerated catalyst from regenerator 6 is split into two streams: one strand (defined as regenerated catalytic cracking catalyst I) is introduced into the first reactor 1 from a first regeneration inclined pipe 12, and the preheated raw material is contacted with the hot regenerated catalytic cracking catalyst I at the lower part of the first reactor 1 to carry out a first catalytic cracking reaction; the other stream (defined as regenerated catalytic cracking catalyst II) leaves regenerator 6 and passes through heat exchange means 7 to be heated and then introduced into second reactor 2. The material flow from the first reactor 1 and the material flow from the second reactor enter a third reactor 3 together to carry out a third catalytic cracking reaction; the material flow obtained after the third catalytic cracking reaction is separated in the settler 4 through the middle gas-solid separator 41, the gas product leaves the reactor for subsequent treatment, and the spent catalyst enters the stripper 5 positioned below and then enters the regenerator 6 for regeneration.

Fig. 2 is a schematic structural diagram of an apparatus for catalytically converting a heavy petroleum hydrocarbon feedstock according to another preferred embodiment of the present invention, i.e., a heat exchanger 7 is externally connected to heat the regenerated catalyst, and the regenerated catalytic cracking catalyst II is directly led out from the bottom of the heat exchanger 7 and conveyed to the second reactor 2.

The invention also has the following specific advantages:

the operation flexibility of the device is improved through smaller modification, and the switching between a mode of producing more low-carbon olefins and a mode of producing more gasoline can be realized; the temperature and the flow of the regenerated catalytic cracking catalyst II are controlled, so that the reaction condition of the third reactor can be accurately regulated and controlled, and the product composition can be flexibly regulated.

The present invention will be described in detail below by way of examples. In the following examples, the raw materials used are all commercially available ones unless otherwise specified.

The properties of the heavy petroleum hydrocarbon feedstock I used in the examples are listed in Table 1, and the properties of the light petroleum hydrocarbon feedstock I are listed in Table 2

The catalytic cracking catalyst is MMC-2 type catalyst and MLC-500 type catalyst produced by Qilu catalyst division of China petrochemical company Limited.

Example 1

The preheated heavy petroleum hydrocarbon raw material is atomized by water vapor and then is introduced into the lower part of a first (lifting pipe) reactor, and contacts with a hot regenerated catalytic cracking catalyst I from a regenerator to carry out a first catalytic cracking reaction;

the regenerated catalytic cracking catalyst II (shown as a second catalyst in the table) flows through a tubular heat exchanger after leaving the regenerator, exchanges heat with water and is then introduced into a second riser pipe serving as a catalyst conveying pipe;

the oil gas product and the catalyst from the first (riser) reactor and the regenerated catalytic cracking catalyst II after heat extraction from the second riser enter a third (fluidized bed) reactor together for carrying out a third catalytic cracking reaction. And the spent catalyst and the oil gas product which leave the third reactor enter a gas-solid separator, the gas product leaves the third reactor for subsequent treatment, and the spent catalyst enters a stripper positioned below and then enters a regenerator.

The catalyst of this example was MLC-500.

The operating conditions, product distribution are listed in table 3 and the properties of the gasoline product are listed in table 4.

Example 2

This example is the same as the procedure and catalyst of example 1, except that the heat transfer zone through which the regenerated catalytic cracking catalyst II exits the regenerator is a set of cooling medium nozzles, the cooling medium is water, and the weight ratio of the injected amount of cooling medium to the second catalyst is 1: 10.

Example 3

The present example is the same as the flow and catalyst of example 2, except that the injected cooling medium is the dry gas produced by the apparatus itself, and the mass ratio of the injected cooling medium to the second catalyst is 1: 1. the operating conditions, product distribution are listed in table 3 and the properties of the gasoline product are listed in table 4.

Comparative example 1

The comparative example adopts a conventional catalytic cracking mode, preheated heavy petroleum hydrocarbon raw material is introduced into the lower part of a first (lifting pipe) reactor after being atomized by water vapor, and is contacted with hot regenerated catalytic cracking catalyst I from a regenerator to carry out a first catalytic cracking reaction, the obtained oil gas product directly enters a gas-solid separator, the gas product leaves the reactor for subsequent treatment, and the spent catalyst enters a stripper positioned below and then enters the regenerator.

The catalyst of this comparative example was MLC-500.

Comparative example 2

The comparative example adopts an MIP process mode, preheated heavy petroleum hydrocarbon raw material is atomized by water vapor and then introduced into the lower part of a series-connection reducing riser reactor, the heavy petroleum hydrocarbon raw material is contacted with hot regenerated catalytic cracking catalyst I from a regenerator to carry out first catalytic cracking reaction, the obtained oil gas product directly enters a gas-solid separator, the gas product leaves the reactor to carry out subsequent treatment, and the spent catalyst enters a stripper positioned below and then enters the regenerator.

The catalyst of this comparative example was MLC-500.

Example 4

the regenerated catalytic cracking catalyst II is directly introduced into a second (riser) reactor (fresh raw materials are not introduced into the reactor for catalytic cracking reaction) after leaving the regenerator;

the oil gas product and the catalyst from the first (riser) reactor and the regenerated catalytic cracking catalyst II after heat extraction from the second (riser) reactor enter a third (fluidized bed) reactor together for carrying out a third catalytic cracking reaction. And the spent catalyst and the oil gas product which leave the third reactor enter a gas-solid separator, the gas product leaves the third reactor for subsequent treatment, and the spent catalyst enters a stripper positioned below and then enters a regenerator.

The catalyst of this example was MMC-2.

The operating conditions and the product distribution are shown in Table 5.

Example 5

This example was carried out using a similar process to that of example 4, except that in this example a light petroleum hydrocarbon feedstock I of the nature shown in Table 2 was introduced into the second reactor.

The catalyst of this example was MMC-2.

The specific operating conditions and product distribution are shown in Table 5.

Comparative example 3

The preheated heavy petroleum hydrocarbon raw material is atomized by water vapor and then is introduced into the lower part of a first (lifting pipe) reactor, and contacts with a hot regenerated catalytic cracking catalyst I from a regenerator to carry out a first catalytic cracking reaction; the oil gas product and the catalyst from the first (riser) reactor enter a third (fluidized bed) reactor to carry out a third catalytic cracking reaction.

And the spent catalyst and the oil gas product which leave the third reactor enter a gas-solid separator, the gas product leaves the third reactor for subsequent treatment, and the spent catalyst enters a stripper positioned below and then enters a regenerator.

The catalyst of this comparative example was MMC-2.

The operating conditions and the product distribution are shown in Table 5.

TABLE 1

TABLE 2

	Light petroleum hydrocarbon feedstock I
		Density at 20 ℃ in kg/m³	699.7
Atmospheric distillation range (gasoline)
		Initial boiling point	34
5％	40
		10％	41
30％	42
		50％	46
70％	51
		90％	68
95％	75
		End point of distillation	89
Composition of hydrocarbons, wt.%
		N-alkanes	1.71
Isoalkanes	4.94
		Olefins	6.19
Cycloalkanes	1.55
		Aromatic hydrocarbons	85.61

TABLE 3

	Example 1	Example 2	Example 3	Comparative example 1	Comparative example 2
						Reaction temperature of
First riser	550	550	550	530	550
						Outlet of the second riser	450	460	480	/	/
Fluidized bed	510	514	522	/	/
						The second catalyst accounts for the mass fraction of the total catalyst	40％	40％	40％	/	/
Dose-to-oil ratio (one inverse)	6.5	6.5	6.5	6	6.4
						Water-oil ratio (one inverse)	0.1	0.1	0.1	0.1	0.1
Reaction time (one reaction)/s	2.5	2.5	2.5	2.8	2.6
						Absolute pressure (settler top pressure) MPa of reaction zone	0.30	0.35	0.32	0.33	0.32
Weight hourly space velocity (three reaction) h^-1	10	10	10	/	/
						Distribution of the product, weight%
Dry gas	3.88	3.75	3.39	3.23	3.64
						Liquefied gas	14.36	13.56	13.72	13.48	13.19
Gasoline (gasoline)	44.93	45.62	45.58	45.68	43.51
						Diesel oil	23.89	24.33	25.06	25.79	27.00
Heavy oil	4.55	4.89	5.06	3.04	4.03
						Coke	8.39	7.85	7.19	8.78	8.63
Total of	100	100	100	100	100

TABLE 4

TABLE 5

	Example 4	Example 5	Comparative example 3
				Reaction temperature of
Outlet of the first riser	560	560	590
				Outlet of the second riser	720	640
Fluidized bed	580	580	580
				The second catalyst accounts for the mass fraction of the total catalyst	15％	30％	/
Dose-to-oil ratio (one inverse)	14	14	14
				Dose-oil ratio (Erlang)		20
Water-oil ratio (one inverse)	0.3	0.3	0.3
				Reaction time (one reaction)/s	2	2	2
Absolute pressure (settler top pressure) MPa of reaction zone	0.21	0.22	0.20
				Weight hourly space velocity (three reaction) h^-1	6.6	6.2	8
Distribution of the product, weight%
				Dry gas	11.48	10.76	12.33
Liquefied gas	39.16	42.16	35.33
				Gasoline (gasoline)	26.17	22.33	26.81
Diesel oil	11.39	12.85	11.53
				Heavy oil	3.07	4.67	4.28
Coke	8.73	7.23	9.72
				Yield of propylene,% by weight	100	100	100

From the above results, it can be seen that the present invention, when used as a process for producing gasoline from heavy oil, can achieve gasoline yield and gasoline quality comparable to or even slightly higher than those of the prior art with high yield and high octane number; when the method is used for producing the low-carbon olefin from the heavy oil, the high propylene yield can be obtained, and the method has the advantage of flexible conversion.

The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims

1. A process for the catalytic conversion of a heavy petroleum hydrocarbon feedstock in an apparatus comprising a first reactor, a second reactor, a third reactor, a settler and a regenerator, the process comprising:

2. The method of claim 1, wherein the method is a method for catalyzing the heavy petroleum hydrocarbon feedstock to produce higher yields of lower olefins, and the second reactor is a reactor for performing catalytic cracking reactions.

3. The method of claim 2, wherein the method further comprises: and carrying out a second catalytic cracking reaction on the light petroleum hydrocarbon raw material I and the regenerated catalytic cracking catalyst II in the second reactor.

4. The method of claim 1, wherein the method is a method for catalyzing the heavy petroleum hydrocarbon feedstock to produce higher yields of lower olefins, and the second reactor is a transport pipe.

5. The method as claimed in any one of claims 1 to 4, wherein the method is a method for producing more light olefins from the heavy petroleum hydrocarbon feedstock by catalysis, the reaction temperature of the first reactor is 480-620 ℃, and the reaction temperature of the third reactor is 500-650 ℃;

preferably, the outlet temperature of the second reactor is 550-750 ℃.

6. The process of claim 1, wherein the process is a process for the catalytic upgrading of the heavy petroleum hydrocarbon feedstock to gasoline, the second reactor being a transfer pipe;

preferably, the reaction temperature of the first reactor is 480-560 ℃, the temperature of the outlet of the second reactor is 400-540 ℃, and the reaction temperature of the third reactor is 450-550 ℃.

7. The process of any of claims 1-6, wherein the first reactor and the second reactor are riser reactors and the third reactor is a fluidized bed reactor.

8. The method according to any one of claims 1 to 7, wherein the method is a method for catalyzing the heavy petroleum hydrocarbon feedstock to produce gasoline in a high yield, and the spent catalyst circulated as the regenerated catalytic cracking catalyst II is introduced into the second reactor after being led out from the regenerator and subjected to heat exchange in a heat remover for cooling;

preferably, the heat collector is an external heat exchanger.

9. The process according to any one of claims 1-8, wherein the heavy petroleum hydrocarbon feedstock I is a grease and/or a heavy hydrocarbon selected from at least one of diesel, hydrogenated tail oil, vacuum gas oil, crude oil, residual oil, coal liquefaction oil, oil sand oil, and shale oil.

10. The process of claim 3, wherein the light petroleum hydrocarbon feedstock I is selected from at least one of cracked light gasoline and cracked C4 hydrocarbon components;

preferably, the cracked light gasoline and/or the cracked C4 hydrocarbon components are subjected to hydrogenation reaction to remove dienes and alkynes and then are introduced into the second reactor.

11. A device for catalytic conversion of heavy petroleum hydrocarbon raw materials is characterized by comprising a first reactor (1), a second reactor (2), a third reactor (3), a settler (4), a gas-solid separator (41), a stripper (5) and a regenerator (6),

the first reactor (1) is coaxial and in communication with the third reactor (3), the settler (4) with the gas-solid separator (41) contained therein, the stripper (5);

the settler (4) is located above the third reactor (3); the stripper (5) is located below the third reactor (3); one end of the first reactor is opened and positioned in the third reactor (3);

the second reactor (2) is positioned outside the stripper (5), one end of the second reactor (2) penetrates through the outer wall of the settler (4) and extends into the interior of the settler (4), and at least one opening of the second reactor (2) is positioned at the upper part of the third reactor (3);

the stripper (5) is in communication with the regenerator (6) by means of a line, and the regenerator (6) is also in communication with the first reactor (1) and the second reactor (2) by means of a line, respectively; and a pipeline for communicating the regenerator (6) with the second reactor (2) is provided with or externally connected with heat exchange equipment.

12. The process according to claim 11, wherein the first reactor (1) and the second reactor (2) are riser reactors and the third reactor (3) is a fluidized bed reactor.