CN115873625A - Method for reducing carbon dioxide emission in catalytic cracking - Google Patents
Method for reducing carbon dioxide emission in catalytic cracking Download PDFInfo
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- CN115873625A CN115873625A CN202111145729.4A CN202111145729A CN115873625A CN 115873625 A CN115873625 A CN 115873625A CN 202111145729 A CN202111145729 A CN 202111145729A CN 115873625 A CN115873625 A CN 115873625A
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- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 49
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 10
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 100
- 238000006243 chemical reaction Methods 0.000 claims abstract description 58
- 230000008929 regeneration Effects 0.000 claims abstract description 58
- 238000011069 regeneration method Methods 0.000 claims abstract description 58
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- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 14
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 59
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 55
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- 239000003502 gasoline Substances 0.000 claims description 4
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- 230000035484 reaction time Effects 0.000 claims description 3
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- 238000002485 combustion reaction Methods 0.000 description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 7
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
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- 239000003513 alkali Substances 0.000 description 2
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 2
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- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
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- GZGREZWGCWVAEE-UHFFFAOYSA-N chloro-dimethyl-octadecylsilane Chemical compound CCCCCCCCCCCCCCCCCC[Si](C)(C)Cl GZGREZWGCWVAEE-UHFFFAOYSA-N 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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Abstract
The present application provides a method for reducing carbon dioxide emissions in catalytic cracking, comprising: the hydrocarbon oil raw material and the catalytic cracking catalyst are contacted in a catalytic cracking reactor and subjected to catalytic cracking reaction, reaction oil gas and the carbon deposit spent catalyst are separated, and the reaction oil gas is sent to a subsequent separation system; and (3) regenerating the spent catalyst after steam stripping, wherein the regeneration is carried out in a regeneration device, and the obtained regenerated catalyst is conveyed to the catalytic cracking reactor. The method can greatly reduce CO on the premise of not influencing the coking effect of the catalyst 2 Discharging and producing CO.
Description
Technical Field
The present invention relates to the catalytic cracking of petroleum hydrocarbons, and more particularly to a process for the production of carbon monoxide to reduce carbon dioxide emissions using a catalytic cracking regeneration process.
Background
The catalytic cracking of petroleum raw material is an important petroleum refining process, and the catalytic cracking device mainly comprises a catalytic cracking reactor and a catalyst regenerator. In catalyst regenerators, usingThe regeneration gas regenerates the catalyst deposited with carbon and generates regeneration flue gas. During regeneration of the catalyst, coke is burned to produce a large amount of CO 2 Gas, making the catalytic cracker the largest CO of the refinery 2 Emission source, CO in catalytic cracking flue gas 2 Accounting for 15 to 50 percent of the total amount of the refinery emission. 211.7kgCO discharged by a catalytic cracking unit for processing each ton of raw materials 2 About 190 sets of catalytic cracking units in China, the total processing capacity is about 2.1 million tons/year, and at least 4000 million tons of CO exist 2 And (4) discharging the amount.
In the regeneration process of the catalyst, a large amount of generated heat makes the heat of the catalytic device surplus, an external heating device is needed to convert the heat generated by the regeneration of the catalyst into steam energy, and the high-temperature flue gas is subjected to energy recovery, but the heat is low-quality energy utilization. And the regeneration flue gas contains carbon monoxide, and the carbon monoxide can cause tail combustion, so that the local overheating of the regenerator and the inactivation of the catalyst are aggravated. The tail combustion can be reduced by controlling the content of oxygen in the flue gas, but the burning rate and the burning strength can be reduced, and the problem of tail gas emission is also caused, so that the loss of chemical energy in carbon monoxide is caused. Carbon monoxide combustion improver or a flue gas boiler is often used in refineries to reduce carbon monoxide in flue gas and recover energy, but the problem of carbon monoxide in flue gas is not solved properly all the time.
CN1400159A discloses a method for producing hydrogen by using catalytic cracking regenerated flue gas, which can reasonably utilize CO in the regenerated flue gas and alleviate the problem of excess heat of an FCC device. However, the CO content obtained by this method is low, reaching only about 14 v%.
CN10269881 a discloses a pure oxygen regeneration process and a hydrogen production method of a fluid catalytic cracking catalyst, which can significantly improve the energy utilization quality and efficiency, reduce the energy consumption and pollutant emission of an FCC regeneration system, and simultaneously make the generated CO prepare hydrogen through a water gas shift reaction.
CN101457152A discloses a hydrocarbon oil conversion method, in the regeneration process, the spent catalyst is contacted with water vapor and oxygen-containing gas in a gasification furnace to obtain synthesis gas and semi-regenerated catalyst. The method can increase the yield of carbon monoxide and hydrogen, and carbon monoxide can be converted into hydrogen in the subsequent processing process, thereby obtaining higher hydrogen yield.
However, in the prior art, hydrogen is produced by incompletely regenerating flue gas, although coke is utilized, carbon is still mainly discharged in the form of carbon dioxide, and the content of CO is low; the method for preparing synthesis gas by directly contacting spent catalyst with steam can accelerate the deactivation of the catalyst.
Disclosure of Invention
The application provides a method for reducing carbon dioxide emission in catalytic cracking, which comprises the following steps:
the hydrocarbon oil raw material and the catalytic cracking catalyst are contacted in a catalytic cracking reactor to carry out catalytic cracking reaction, reaction oil gas and the carbon deposit spent catalyst are separated, and the reaction oil gas is sent to a subsequent separation system;
the spent catalyst is regenerated after being stripped, the regeneration is carried out in a regeneration device, and the obtained regenerated catalyst is conveyed to the catalytic cracking reactor;
wherein the regeneration device comprises a first regenerator and a second regenerator, the regeneration comprising:
enabling the spent catalyst to be in contact with a first oxygen-containing gas in the first regenerator to carry out a first regeneration reaction to obtain a semi-regenerated catalyst, leading first flue gas out of the first regenerator, and separating to obtain a CO product;
contacting the semi-regenerated catalyst with a second oxygen-containing gas in a second regenerator for second regeneration to obtain a regenerated catalyst and generate a second flue gas;
wherein part or all of the first oxygen-containing gas is the second flue gas; wherein the first regeneration reaction conditions in the first regenerator comprise: the reaction temperature is 400-600 ℃, and the average residence time of the spent catalyst is 2-10 minutes.
In one embodiment, the first regeneration reaction conditions in the first regenerator comprise: the reaction temperature is 500-550 ℃, the gas apparent linear speed is 0.3-5 m/s, and the average residence time of the spent catalyst is 5-10 minutes.
In one embodiment, the first regenerator is a downer reactor, and the first oxygen-containing gas and the spent catalyst both enter the first regenerator from the top of the first regenerator.
In one embodiment, the regeneration unit further comprises a gas-solid separator for separating the first flue gas produced by the first regenerator from the semi-regenerated catalyst.
In one embodiment, the second regeneration reaction conditions in the second regenerator comprise: the reaction temperature is 600-750 ℃, the gas apparent linear speed is 0.3-5 m/s, and the average residence time of the spent catalyst is 0.6-5 minutes.
In one embodiment, the second oxygen-containing gas is selected from the group consisting of oxygen, air, a mixture of oxygen and nitrogen having an oxygen content of 10 to 30%, oxygen and CO having an oxygen content of 10 to 30% 2 The mixed gas of (1).
In one embodiment, the catalytic cracking reactor is a riser reactor, a fluidized bed reactor, or a combination thereof.
In one embodiment, the reaction conditions for catalytic cracking of the hydrocarbon oil feedstock include: the reaction temperature is 450-700 ℃, the reaction time is 1-10 seconds, the ratio of the catalyst to the oil is 1-50: 1, the airspeed is 0.5 to 20h -1 。
In one embodiment, the hydrocarbon oil feedstock comprises a petroleum hydrocarbon selected from one or more of gasoline, diesel oil, vacuum wax oil, atmospheric wax oil, coker wax oil, deasphalted oil, vacuum residue, atmospheric residue, raffinate oil, and low grade recycle oil, and/or other mineral oils selected from one or more of coal liquefaction oil, oil sand oil, and shale oil.
In the invention, the burning of coke in the catalyst regeneration process is controlled to generate CO by incomplete combustion, and the CO in the catalytic device can be greatly reduced by controlling the regeneration condition 2 Discharging, at the same time, CO in the first oxygen-containing gas 2 Can react with coke to generate CO, further reduce CO 2 And the emission is realized, and the content of CO in the flue gas is obviously improved. The generated CO can be the raw material of the subsequent chemical industry, metallurgy and the like, and the production is savedCoal, methane and other raw materials of CO, resources and energy consumption are saved, and emission is further reduced. Therefore, under the background of carbon neutralization and carbon peak-reaching targets, CO produced in the catalytic cracking regeneration process can be changed into valuable, energy conservation and emission reduction can be realized, and great economic benefits and social benefits are achieved.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a schematic flow diagram according to an embodiment of the present invention.
Fig. 2 is a schematic flow diagram according to a preferred embodiment of the present invention.
FIG. 3 is a schematic of a catalytic cracking scheme with a single stage regeneration.
Detailed Description
The present application is described in further detail below with reference to the figures and examples. The features and advantages of the present application will become more apparent from the description.
The word "exemplary" is used exclusively herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments. While the various aspects of the embodiments are presented in drawings, the drawings are not necessarily drawn to scale unless specifically indicated.
In addition, the technical features described below in the different embodiments of the present application may be combined with each other as long as they do not conflict with each other.
The application provides a method for reducing carbon dioxide emission in catalytic cracking, which comprises the following steps:
the hydrocarbon oil raw material and the catalytic cracking catalyst are contacted in a catalytic cracking reactor to carry out catalytic cracking reaction, reaction oil gas and the carbon deposit spent catalyst are separated, and the reaction oil gas is sent to a subsequent separation system;
the spent catalyst is regenerated after being stripped, the regeneration is carried out in a regeneration device, and the obtained regenerated catalyst is conveyed to the catalytic cracking reactor;
wherein the regeneration device comprises a first regenerator and a second regenerator, the regeneration comprising:
enabling the spent catalyst to contact with a first oxygen-containing gas in the first regenerator to carry out a first regeneration reaction to obtain a semi-regenerated catalyst, leading out first flue gas from the first regenerator, and separating to obtain a CO product;
contacting the semi-regenerated catalyst with a second oxygen-containing gas in a second regenerator for second regeneration to obtain a regenerated catalyst and generate a second flue gas;
wherein part or all of the first oxygen-containing gas is the second flue gas.
According to the catalytic cracking method of the present invention, the separation of the spent catalyst and the reaction oil gas, and the separation of the reaction oil gas from the fractions such as dry gas, liquefied gas, stable gasoline, and catalytic diesel oil by the subsequent separation system can be performed by methods of the conventional art, and the present invention is not limited thereto, and will not be described in detail herein.
According to the present invention, the catalytic cracking reactor may be a conventional catalytic cracking riser reactor, a fluidized bed reactor or a combination thereof well known to those skilled in the art, for example, a catalytic cracking riser reactor is connected in series with a fluidized bed reactor. The riser reactor may be selected from an equal diameter riser reactor and/or an equal linear velocity riser reactor, preferably an equal diameter riser is used. The fluidized bed reactor is positioned at the downstream of the riser reactor and is connected with the outlet of the riser reactor, the riser reactor sequentially comprises a pre-lifting section and at least one reaction zone from bottom to top, and in order to ensure that the raw oil can be fully reacted, and the number of the reaction zones can be 2-8, preferably 1-3 according to the quality requirements of different target products.
According to the present invention, the catalytic cracking reaction conditions include: the reaction temperature is 450-700 ℃, preferably 500-650 ℃, and more preferably 550-600 ℃; the time is 1 to 10 seconds, preferably 2 to 5 seconds, the catalyst-to-oil ratio (i.e., the weight ratio of the catalyst to the hydrocarbon oil raw material) is 1 to 50:1, preferably 5 to 30:1; the space velocity is 0.5 to 20 hours -1 Preferably 2 to 10 hours -1 。
In the method provided by the invention, the reactor can also inject water vapor, the water vapor is preferably injected in the form of atomized steam, and the weight ratio of the injected water vapor to the light hydrocarbon oil raw material can be 0.01-1: 1, preferably 0.05 to 0.5:1.
according to the catalytic cracking process of the present invention, preferably the process of the present invention further comprises: before the raw oil is contacted with a catalytic cracking catalyst, the raw oil is preheated to 100-450 ℃ and then is introduced into a reactor to be contacted with the catalytic cracking catalyst, preferably preheated to 150-300 ℃.
According to the catalytic cracking process of the present invention, the catalytic cracking catalyst may be conventionally selected in the art, and for the present invention, it is preferable that the catalytic cracking catalyst comprises 15 to 65% by weight of natural minerals, 10 to 30% by weight of inorganic oxides, and 25 to 75% by weight of zeolite, based on the total weight of the catalyst.
According to the invention, the zeolite is preferably one or more mixtures of Y zeolite, mordenite, beta zeolite, zeolite with MFI structure (for example ZSM series zeolite and/or ZRP zeolite) as active component.
According to the invention, the natural mineral is selected from one or more of kaolin, halloysite, montmorillonite, diatomaceous earth, attapulgite, sepiolite, halloysite, hydrotalcite, bentonite and rectorite.
The inorganic oxide is selected from one or more of silicon oxide, aluminum oxide, zirconium oxide, titanium oxide and amorphous silica-alumina.
According to the catalytic cracking process of the present invention, at least a portion of the catalytic cracking catalyst is regenerated catalyst, preferably all of the catalytic cracking catalyst is regenerated catalyst.
According to the present invention, wherein the feedstock comprises petroleum hydrocarbons selected from one or more of gasoline, diesel oil, vacuum wax oil, atmospheric wax oil, coker wax oil, deasphalted oil, vacuum residue, atmospheric residue, raffinate oil and low grade recycle oil, and/or other mineral oils selected from one or more of coal liquefaction oil, oil sand oil and shale oil.
According to the invention, the reaction temperature of the first regenerator is 400 to 600 ℃, preferably 450 to 580 ℃, more preferably 500 to 550 ℃; the gas apparent linear velocity is 0.3-5 m/s, preferably 0.9-3 m/s, more preferably 1-2.5 m/s; the average residence time of the spent catalyst is between 2 and 10 minutes, preferably between 4 and 8 minutes, more preferably between 5 and 7 minutes. Moreover, the inventors of the present application have also found that the choice of the reaction temperature of the first regenerator and the average residence time of the spent catalyst is very important for controlling the proportion of CO in the regeneration flue gas: under the condition of controlling the carbon-oxygen ratio, the reaction temperature of the first regenerator is reduced, and the residence time of the spent catalyst in the first regenerator is prolonged, so that the ratio of CO in the flue gas is increased. The inventors have found that, at a reaction temperature of 500 to 550 ℃ in the first regenerator and an average residence time of the spent catalyst of 5 to 7 minutes, a high CO content in the flue gas, up to around 80% and even over 90% (with oxygen as the second oxygen-containing gas), is achieved, which is unexpected for the skilled person.
According to the invention, the reaction temperature of the second regenerator is 600 to 750 ℃, preferably 630 to 720 ℃, more preferably 670 to 700 ℃, the gas superficial linear velocity is 0.3 to 5 m/s, preferably 0.9 to 3 m/s, more preferably 1 to 2.5 m/s, and the average residence time of the spent catalyst is 0.6 to 5 minutes, preferably 2 to 4 minutes, more preferably 2.5 to 3.5 minutes.
According to the invention, during the regeneration, the catalyst and the oxygen-containing gas can be in countercurrent contact or in cocurrent contact, and the catalyst can move upwards or downwards.
FIG. 1 illustrates one embodiment of the present application showing countercurrent contact of a catalyst with an oxygen-containing gas. As shown in fig. 1, a catalytic cracking raw oil 1 enters from the bottom of a riser reactor 2, contacts with a regenerated catalyst to react, a reaction oil gas and a catalyst move upwards to a settler 3 for gas-solid separation, and a separated reaction oil gas 4 is sent to a subsequent separation system (not shown) for separation to obtain various products; the spent catalyst obtained by separation in the settler 3 enters a first regenerator 6 through a spent slide valve 5, and is subjected to first regeneration in the presence of first oxygen-containing gas to generate first flue gas 7 and a semi-regenerated catalyst; the regenerated first flue gas 7 goes to a subsequent energy recovery and separation system 8 to obtain carbon monoxide 9 and other flue gas components 16, the semi-regenerated catalyst enters a second regenerator 13 under the conveying of gas 11, and is in contact with a second oxygen-containing gas 12 for second regeneration to obtain a regenerated catalyst and a second flue gas 10; the regenerated catalyst is degassed by a degassing tank 14 and then returns to the bottom of the riser reactor 2 through a regeneration slide valve 15 to contact with the raw oil 1 for reaction; the second flue gas 10 is all returned to the first regenerator 6 as the first oxygen containing gas.
FIG. 2 illustrates another embodiment of the present application showing co-current contacting of the catalyst with an oxygen-containing gas. As shown in fig. 2, a catalytically cracked feedstock oil 21 enters from the bottom of a riser reactor 22, contacts with a regenerated catalyst to react, a reaction oil gas and a catalyst move upwards to a settler 23 for gas-solid separation, a reaction oil gas 24 obtained by separation enters a subsequent separation system (not shown) for separation, an obtained spent catalyst enters the top of a first regenerator 27 through a spent slide valve 25, contacts with a first oxygen-containing gas 26 and moves downwards to perform first regeneration, and then enters a gas-solid separator 210, and a first flue gas 14 obtained by separation enters a subsequent energy recovery and separation system 215 to obtain carbon monoxide 216 and other flue gas components 217; the separated semi-regenerated catalyst enters a second regenerator 28 to contact with a second oxygen-containing gas 212 for second regeneration and moves upwards together, the semi-regenerated catalyst enters a cyclone separator 29 for gas-solid separation, the separated second flue gas 26 completely enters a first regenerator 27, and the separated regenerated catalyst returns to the bottom of the riser reactor 22 through a regeneration slide valve 211 after being degassed by a degassing section 213 to contact with the raw oil 21 for reaction.
In the embodiment shown in fig. 2, the first regenerator 26 may be a downer reactor, and the first oxygen-containing gas and the spent catalyst both enter the first regenerator 26 from the top of the first regenerator 26. With this form of downer reactor as the first regenerator, a large C/O ratio (atomic carbon/oxygen ratio) can be achieved, thereby increasing the CO content in the first flue gas.
According to the invention, the second oxygen-containing gas may be oxygen, air, a mixture of oxygen and nitrogen having an oxygen content of 10-30%, and/or oxygen and CO having an oxygen content of 10-30% 2 The mixed gas of (3), preferably oxygen, more preferably oxygen and CO containing 10 to 30% of oxygen 2 The mixed gas of (1). According to the invention, the oxygen and CO with the oxygen content of 10-30 percent 2 CO in the mixed gas 2 Can be derived from CO in the regenerated flue gas 2 。
According to the catalytic cracking method of the present invention, it is preferable that the method of the present invention further comprises stripping (generally steam stripping) the regenerated catalyst obtained by the second regeneration to remove impurities such as gas.
According to the invention, the CO can be separated by alkali washing, membrane separation, pressure swing adsorption, cryogenic process, COSORB process or other separation and purification methods known to those skilled in the art, preferably alkali washing. According to the invention, before CO is separated, the flue gas can be purified to remove impurities such as sulfur oxides, nitrogen oxides and the like.
The method provided by the invention is used for producing carbon monoxide by changing a regenerative burning mode, the catalyst is not contacted with high-temperature steam, the inactivation of the catalyst is not accelerated, tail combustion can be effectively reduced, and the inactivation rate of the catalyst is slowed down.
The method provided by the invention reduces the heat release of combustion and relieves the problem of excessive heat of the catalytic device through incomplete combustion. The method provided by the invention can completely regenerate the spent catalyst in the second regenerator without influencing the catalytic cracking reaction activity.
When the method provided by the invention adopts oxygen as the oxygen source for burning, nitrogen is not introduced, and a simpler method can be adopted to separate and obtain a CO product with higher purity. When oxygen and CO are used 2 When the mixed gas of (A) is used as an oxygen source, part of CO can be generated 2 Conversion to CO and enrichment of CO 2 The carbon capture and utilization are facilitated. When pure oxygen is used as the oxygen-containing regeneration gas, the volume ratio of CO in the flue gas can reach more than 76 percent; when air is used as the oxygen-containing regeneration gas, the flue gasThe volume ratio of CO can reach more than 24 percent; also, oxygen and CO may be used 2 The mixed gas of the gases is used as oxygen-containing regeneration gas, and the volume ratio of CO in the flue gas can reach more than 80%.
The method provided by the invention has low regeneration temperature and can realize large catalyst-oil ratio operation of catalytic cracking reaction.
The method provided by the invention not only reduces the emission of carbon dioxide of the catalytic device, but also can generate high-content carbon monoxide as a raw material of a subsequent chemical process, thereby realizing the purposes of changing waste into valuable and fully utilizing resources, saving fossil resources such as coal, oil and methane for producing carbon monoxide, reducing energy consumption and investment, reducing pollution and improving economic benefits and social benefits of the petrochemical industry.
The following examples further illustrate the process but do not limit the invention.
The stock oil used in the examples and comparative examples was an Anqing wax oil, and its properties are shown in Table 1.
The catalytic cracking catalysts used in the examples and comparative examples were sold under the trade name CDOS (Changling division, china petrochemical catalyst Co., ltd.).
Examples 1 to 5
The experiment was carried out according to the scheme of FIG. 2, and the relevant operating conditions and products are listed in Table 2.
Example 6
The experiment was carried out according to the scheme of FIG. 1, the relevant operating conditions and the products are listed in Table 2
Comparative examples 1 to 2
The experiment was carried out according to the scheme of FIG. 1, the relevant operating conditions and products being listed in Table 3.
Comparative examples 3 to 4
The experiment was carried out according to the scheme of FIG. 2, and the relevant operating conditions and products are listed in Table 3.
Comparative examples 5 to 6
According to the flow shown in the attached figure 3, a catalytic cracking raw oil 31 enters from the bottom of a riser reactor 32 and contacts with a regenerated catalyst to react, a reaction oil gas and the catalyst move upwards to a settler 33 for gas-solid separation, the separated reaction oil gas 34 enters a subsequent absorption stabilizing system, a spent catalyst enters a regenerator 36 through a spent slide valve 35 to contact with oxygen-containing gas for regeneration, regenerated flue gas 37 is led out of the regenerator 36 to a subsequent energy recovery system, and the regenerated catalyst returns to the bottom of the riser reactor 32 through a regenerated slide valve 39 to contact with the raw oil 31 for reaction. The relevant operating conditions and products are listed in table 3.
It can be seen from the results of the examples that the method of the present invention has advantages of greatly reducing carbon dioxide emissions and producing carbon monoxide.
The present application has been described above with reference to preferred embodiments, but these embodiments are merely exemplary and merely illustrative. On the basis of the above, the present application can be subjected to various substitutions and modifications, which are all within the scope of protection of the present application.
TABLE 1
TABLE 2
TABLE 3
| Item | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 |
| Reaction conditions | ||||||
| Reaction temperature/. Degree.C | 550 | 550 | 550 | 550 | 550 | 550 |
| Ratio of agent to oil | 8 | 8 | 8 | 8 | 8 | 8 |
| Reaction time/ |
3 | 3 | 3 | 3 | 3 | 3 |
| First regenerator Condition | ||||||
| Regeneration temperature/. Degree.C | 650 | 650 | 650 | 650 | 650 | 650 |
| Catalyst residence time/ |
5 | 5 | 2 | 5 | 5 | 5 |
| Air speed (m/s) | 1.1 | 1.1 | 1 | 0.8 | 1.1 | 1.1 |
| Second regenerator Condition | ||||||
| Regeneration temperature/. Degree.C | 650 | 650 | 650 | 650 | - | - |
| Catalyst residence time/ |
3 | 3 | 3 | 3 | - | - |
| Air speed (m/s) | 1.2 | 1.2 | 1.2 | 1.2 | ||
| Composition of a second oxygen-containing gas | ||||||
| CO 2 | - | - | - | - | - | - |
| O 2 | 100.00 | 21.00 | 100.00 | 100.00 | 21.00 | 100.00 |
| N 2 | - | 79.00 | - | - | 79.00 | - |
| A second smoke composition | ||||||
| CO | 70.99 | 11.50 | 62.4 | 68.37 | 11.56 | 45.83 |
| CO 2 | 28.71 | 11.78 | 37.22 | 31.29 | 13.64 | 53.84 |
| O 2 | 0.02 | 2.26 | 0.17 | 0.09 | 0.21 | 0.08 |
| N 2 | 0.28 | 74.46 | 0.21 | 0.25 | 74.59 | 0.25 |
Claims (9)
1. A method for reducing carbon dioxide emissions in catalytic cracking, comprising:
the hydrocarbon oil raw material and the catalytic cracking catalyst are contacted in a catalytic cracking reactor and subjected to catalytic cracking reaction, reaction oil gas and the carbon deposit spent catalyst are separated, and the reaction oil gas is sent to a subsequent separation system;
the spent catalyst is regenerated after being stripped, the regeneration is carried out in a regeneration device, and the obtained regenerated catalyst is conveyed to the catalytic cracking reactor;
wherein the regeneration device comprises a first regenerator and a second regenerator, the regeneration comprising:
enabling the spent catalyst to be in contact with a first oxygen-containing gas in the first regenerator to carry out a first regeneration reaction to obtain a semi-regenerated catalyst, leading first flue gas out of the first regenerator, and separating to obtain a CO product;
contacting the semi-regenerated catalyst with a second oxygen-containing gas in a second regenerator to carry out second regeneration to obtain a regenerated catalyst and generate a second flue gas;
wherein part or all of the first oxygen-containing gas is the second flue gas; wherein the first regeneration reaction conditions in the first regenerator comprise: the reaction temperature is 400-600 ℃, and the average residence time of the spent catalyst is 2-10 minutes.
2. The method of claim 1, wherein the first regeneration reaction conditions in the first regenerator comprise: the reaction temperature is 500-550 ℃, the gas apparent linear speed is 0.3-5 m/s, and the average residence time of the spent catalyst is 5-10 minutes.
3. The process of claim 1, wherein the first regenerator is a downer reactor, and the first oxygen-containing gas and the spent catalyst both enter the first regenerator from the top of the first regenerator.
4. The method of claim 3, wherein the regeneration device further comprises a gas-solid separator for separating the first flue gas produced by the first regenerator from the semi-regenerated catalyst.
5. The method of claim 1, wherein the second regeneration reaction conditions in the second regenerator comprise: the reaction temperature is 600-750 ℃, the gas apparent linear speed is 0.3-5 m/s, and the average residence time of the spent catalyst is 0.6-5 minutes.
6. The method of claim 5, wherein the second oxygen-containing gas is selected from the group consisting of oxygen, air, a mixture of oxygen and nitrogen having an oxygen content of 10-30%, oxygen and CO having an oxygen content of 10-30% 2 The mixed gas of (1).
7. The process of claim 1, wherein the catalytic cracking reactor is a riser reactor, a fluidized bed reactor, or a combination thereof.
8. The process as claimed in claim 1, wherein the reaction conditions for catalytic cracking of the hydrocarbon oil feedstock comprise: the reaction temperature is 450-700 ℃, the reaction time is 1-10 seconds, the ratio of the catalyst to the oil is 1-50: 1, the airspeed is 0.5 to 20 hours -1 。
9. The process of claim 1, wherein the hydrocarbon oil feedstock comprises petroleum hydrocarbons selected from one or more of gasoline, diesel, vacuum wax, atmospheric wax, coker wax, deasphalted oil, vacuum residuum, atmospheric residuum, raffinate and low grade recycle oils, and/or other mineral oils selected from one or more of coal liquefaction oil, oil sand oil and shale oil.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1400159A (en) * | 2001-07-31 | 2003-03-05 | 中国石油化工股份有限公司 | Hydrogen-making method by utilizing catalytic cracked regenerated flue gas |
| CN1546610A (en) * | 2003-12-05 | 2004-11-17 | 清华大学 | A descending catalytic cracking/cracking reactor for processing heavy raw oil |
| CN103721765A (en) * | 2012-10-12 | 2014-04-16 | 中国石油化工股份有限公司 | Catalyst regeneration method capable of reducing carbon dioxide discharge |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1400159A (en) * | 2001-07-31 | 2003-03-05 | 中国石油化工股份有限公司 | Hydrogen-making method by utilizing catalytic cracked regenerated flue gas |
| CN1546610A (en) * | 2003-12-05 | 2004-11-17 | 清华大学 | A descending catalytic cracking/cracking reactor for processing heavy raw oil |
| CN103721765A (en) * | 2012-10-12 | 2014-04-16 | 中国石油化工股份有限公司 | Catalyst regeneration method capable of reducing carbon dioxide discharge |
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