CN113800996A - Method for preparing light olefin by microwave-driven crude oil catalytic cracking - Google Patents
Method for preparing light olefin by microwave-driven crude oil catalytic cracking Download PDFInfo
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- 150000001336 alkenes Chemical class 0.000 title claims abstract description 75
- 239000010779 crude oil Substances 0.000 title claims abstract description 73
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 39
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- 239000000047 product Substances 0.000 claims abstract description 27
- 238000000926 separation method Methods 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 8
- 239000006227 byproduct Substances 0.000 claims abstract description 8
- 238000001704 evaporation Methods 0.000 claims abstract description 8
- 230000008020 evaporation Effects 0.000 claims abstract description 8
- 230000018044 dehydration Effects 0.000 claims abstract description 6
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 6
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 6
- 125000004122 cyclic group Chemical group 0.000 claims description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 4
- 150000002500 ions Chemical group 0.000 claims description 4
- 238000004064 recycling Methods 0.000 claims description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 238000007670 refining Methods 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 229910016978 MnOx Inorganic materials 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 238000005336 cracking Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000004230 steam cracking Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
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- 238000004587 chromatography analysis Methods 0.000 description 2
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- -1 ethylene, propylene Chemical group 0.000 description 2
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
- C07C4/06—Catalytic processes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
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- C07C2523/32—Manganese, technetium or rhenium
- C07C2523/34—Manganese
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/20—Carbon compounds
- C07C2527/22—Carbides
- C07C2527/224—Silicon carbide
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
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Abstract
The invention discloses a method for preparing light olefin by microwave-driven crude oil catalytic cracking, which comprises the steps of enabling a crude oil raw material to enter a dehydration and metal ion unit, preheating to enter a crude oil flash evaporation unit after dehydration and metal ion removal, cutting crude oil into heavy fraction and light fraction, extracting the light fraction from the top of the flash evaporation unit, enabling the light fraction to enter a microwave catalytic cracking reaction unit, enabling light fraction steam to be in contact with a catalyst, heating to 100-350 ℃ under microwave irradiation, carrying out catalytic cracking reaction, and enabling the light fraction to contain C2-C4 light olefin and byproduct H2The mixed gas flow of C1-C4 alkane enters a product crude separation and unreacted fraction circulating unit, the mixed gas flow is cooled and primary separation is realized, and the unreacted components enter microwavesThe catalytic cracking unit is circulated, and the product is refined. The invention utilizes the synergistic effect of microwave and catalyst, and can crack and generate light olefin at low reaction temperature and high selectivity, thereby realizing the excellent results that the total selectivity of the C2-C4 light olefin is not less than 71 percent and the once-through yield of the light olefin is not less than 31 percent.
Description
Technical Field
The invention belongs to the technical field of crude oil catalytic cracking, and particularly relates to a method for preparing light olefin by microwave-driven crude oil catalytic cracking.
Background
As a key component unit for producing polymer materials such as plastics, rubber and the like, light olefins such as ethylene, propylene and the like play a vital role in the petrochemical industry. The global demand for light olefins such as ethylene and propylene is predicted by authoritative reports to remain rapidly increasing at a rate of 3% per year until 2030. This increasing demand will drive manufacturers to employ new technologies to continuously expand the feedstock range of light olefins while reducing the cost of olefin production. At present, nearly 50% of global ethylene and propylene still adopt a process of naphtha steam cracking production at a high temperature of 800-850 ℃, and as a steam cracking device needs to provide energy through fossil fuel combustion, the naphtha steam cracking process produces CO of ethylene and propylene per ton2The discharge amount is up to 1.6-2 tons. In addition, the high temperature operation of conventional steam cracking processes and the coking of cracking furnace tubes pose significant challenges to the construction and long-term safe operation of cracking equipment.
Therefore, in order to reduce the production cost of light olefins, a technology and a device for producing olefins by direct thermal cracking of crude oil after once flash evaporation are being developed by many international petrochemical companies represented by exxonmobil. The technology for preparing olefin by directly cracking crude oil widens the source of olefin raw materials and shortens the process flow, and has huge economic potential compared with the traditional steam thermal cracking process taking naphtha and gas oil as raw materials.
At the same time, there is a global effort to control CO2Under the large background of emission, the light olefin prepared by cracking crude oil is driven by using a low-carbon energy mode to obviously reduce CO2The discharge is of great significance. Microwaves can be generated from electric energy with high efficiency of about 90 percent, so that in areas with abundant wind and light renewable electric energy resources and huge crude oil resources (such as Saudi Arabia), the technology for producing light olefins by microwave-driven crude oil cracking is developed to realize green, high-efficiency and sustainableLight olefin production and assisted carbon neutralization have important value.
Disclosure of Invention
The invention aims to provide a method for preparing light olefins by microwave-driven crude oil catalytic cracking, which utilizes microwaves as an energy source to drive crude oil catalytic cracking to prepare light olefins.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a method for preparing light olefins by microwave-driven crude oil catalytic cracking comprises the following steps:
the method comprises the following steps that a crude oil raw material firstly enters a dehydration and metal ion unit, is dehydrated and demetallized, and then is preheated and enters a crude oil flash evaporation unit, wherein the feeding temperature is controlled to be 200-350 ℃, and the pressure is controlled to be 70-150 kPa;
in the crude oil flash unit, crude oil is cut into heavy fraction and light fraction, the heavy fraction is extracted from the bottom of the flash unit, and the light fraction is extracted from the top of the flash unit and then enters the microwave catalytic cracking reaction unit;
in a microwave catalytic cracking reaction unit, the light fraction steam is contacted with a catalyst and heated to 100-350 ℃ under microwave irradiation for catalytic cracking reaction to generate a main product of C2-C4 light olefin and a quantitative amount of H as a byproduct2C1-C4 alkane, the mixed gas flow after the microwave catalytic cracking reaction enters a product crude separation and unreacted fraction circulating unit;
in a product crude separation and unreacted fraction recycling unit, the mixed gas flow is cooled and primary separation is realized, wherein C2-C4 light olefins and byproduct H2C1-C4 alkane is extracted from the unit in a gaseous state and is sent to the subsequent olefin refining treatment, unreacted components are circulated to the inlet of the microwave catalytic cracking unit in a liquid state, and are mixed with light fraction steam extracted from the flash evaporation unit according to a certain proportion and then enter the microwave catalytic cracking unit for reaction, so that the cyclic utilization of the unreacted components is realized.
Preferably, the crude oil flash unit is a plate flash tower, the number of theoretical plates of the flash tower is 3-6, isothermal flash operation is carried out, the operating pressure is 2-10 kPa, and the operating temperature is 270-310 ℃.
Preferably, the equipment of the microwave catalytic cracking reaction unit adopts a vertical fixed bed reactor, and the microwave frequency is 900 MHz; or the equipment of the microwave catalytic cracking reaction unit adopts a vertical fluidized bed reactor, and the microwave frequency is 2.45 GHz.
Preferably, when a fixed bed reactor is adopted, the light fraction steam enters from the top of the reactor and flows from top to bottom, and the mass space velocity of the catalytic cracking reaction is kept between 0.4 and 2h-1The corresponding microwave irradiation intensity in the reactor is controlled to be 5-10000 kW/m3Preferably 50 to 3000kW/m3。
Preferably, when a fluidized bed reactor is adopted, light fraction steam enters from the bottom of the reactor and flows from bottom to top, catalyst powder is sprayed from the top of the reactor and flows from top to bottom to form countercurrent flow with the light fraction steam, the mass flow ratio of the light fraction steam to the catalyst powder is controlled to be 0.1-2, the retention time is controlled to be 0.1-10 s, and the corresponding microwave irradiation intensity in the reactor is controlled to be 50-20000 kW/m3Preferably 100 to 5000kW/m3。
Preferably, the catalyst adopted by the microwave catalytic cracking unit is activated carbon, carbon black or a supported carbon catalyst, and the carrier of the supported carbon catalyst is ZSM-5 molecular sieve, SiC or ZrO2、Al2O3、MgO、 Cr2O3、V2O5And one or more of manganese oxide (MnOx), wherein the carbon loading of the supported carbon catalyst is controlled to be 0.5-2.5 wt.%.
Preferably, the particle size of the catalyst is controlled to be 320-50 meshes.
Preferably, the equipment of the product crude separation and unconverted fraction circulating unit is a flash tank, isothermal flash is carried out within the range of 10-40 ℃, and the operating pressure is controlled within 50-500 kPa.
Compared with the prior art, the invention has the following beneficial effects:
1. the microwave is used as an energy source to drive the Saite light crude oil to be selectively cracked on a special catalytic material to generate light olefins such as ethylene, propylene and the like, and the excellent results that the total selectivity of the light olefins from C2 to C4 is not less than 71 percent and the once-through yield of the light olefins is not less than 31 percent can be realized.
2. Compared with the existing naphtha steam cracking process, the process saves the step of distilling crude oil to obtain the naphtha raw material, can greatly shorten the process flow of the production of the petroleum-based light olefin and reduce the equipment investment. In addition, in the invention, the components heavier than naphtha fraction in the crude oil can also be used as raw materials for preparing light olefins by cracking, so that the raw material sources of the light olefins are widened, more fractions in the crude oil can be efficiently and selectively converted into olefin chemicals with higher values compared with fuels, and the utilization value of the crude oil is favorably improved.
3. The operation temperature of the catalytic reaction unit for preparing the light olefin by using the microwave-driven crude oil catalytic cracking can be realized below 350 ℃, and compared with the high temperature of 800-850 ℃ in the naphtha steam thermal cracking process, the process temperature is greatly reduced, so that the great reduction of the process temperature is beneficial to reducing a large amount of energy loss caused by the temperature rise and fall of the process, and is beneficial to improving the energy efficiency of the process.
4. Compared with the prior art, the method has the greatest beneficial effect that the traditional heating cracking process with high energy consumption in the light olefin production process can realize electric drive. Under the current opportunity of rapid growth of renewable electric energy, the microwave-driven light olefin production process derived from the renewable electric energy avoids the massive emission of CO through heat supply of fossil fuel combustion in the traditional heating cracking process2And thus carbon neutralization is extremely favorably achieved.
Drawings
FIG. 1 is a process flow diagram of the method for preparing light olefins by microwave-driven catalytic cracking of crude oil according to the present invention.
FIG. 2 shows the composition of the gaseous products from catalytic cracking of each representative component in crude oil driven by microwaves in fixed bed mode and the corresponding reaction temperature.
FIG. 3 is a graph showing the selectivity of C2-C4 olefins and total light olefins for microwave driven catalytic cracking products of representative components of crude oil in fixed bed mode.
FIG. 4 shows the C2-C4 olefin and total olefin yields and single pass conversion of each component in a fixed bed mode for microwave driven crude oil catalytic cracking of each representative component.
FIG. 5 shows the composition and volume of a gaseous product from the microwave-driven cyclic catalytic cracking of light mixed components (naphtha) in crude oil in a fluidized bed mode.
FIG. 6 is a graph showing the selectivity of C2-C4 olefins and total light olefins for microwave-driven recycle of light mixed components (naphtha) in crude oil catalytically cracked gaseous products in fluidized bed mode.
FIG. 7 shows the gaseous product composition and volume of the cyclic catalytic cracking of fractions before the atmospheric boiling point of 440 ℃ in crude oil driven by microwaves in fluidized bed mode.
FIG. 8 is a graph showing the selectivity of C2-C4 olefins and total light olefins in the gaseous products of catalytic cracking of fractions recycle before the atmospheric boiling point of 440 ℃ in microwave-driven crude oil in fluidized bed mode.
In the figure 1, 1 is crude oil, 2 is a dehydration and metal ion unit, 3 is a crude oil flash evaporation unit, 4 is light fraction, 5 is heavy fraction, 6 is a microwave catalytic cracking reaction unit, 7 is a product crude separation and unreacted fraction circulating unit, 8 is C2-C4 light olefin and byproduct H2C1-C4 alkanes.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples.
The invention provides a method for preparing light olefins by microwave-driven crude oil catalytic cracking, which comprises the following steps as shown in figure 1:
the raw material of crude oil 1 firstly enters a dehydration and metal ion unit 2, is dehydrated and demetallized, and then is preheated to enter a crude oil flash evaporation unit 3, wherein the feeding temperature is controlled to be 200-350 ℃, and the pressure is controlled to be 70-150 kPa;
in a crude oil flash unit 3, crude oil 1 is cut into heavy fraction 5 and light fraction 4, the heavy fraction 5 is extracted from the bottom of the flash unit, and the light fraction 4 is extracted from the top of the flash unit and then enters a microwave catalytic cracking reaction unit 6;
in the microwave catalytic cracking reaction unit 6, the light fraction steam contacts with a catalyst and is heated to 100-350 ℃ under microwave irradiation for catalytic cracking reaction to generateTo obtain the main product of light olefin of C2-C4 and a certain amount of H as a byproduct2C1-C4 alkane, the mixed gas flow after the microwave catalytic cracking reaction enters a product crude separation and unreacted fraction circulating unit 7;
in the product crude separation and unreacted fraction recycling unit 7, the mixed gas flow is cooled and primary separation is realized, wherein C2-C4 light olefins and byproduct H2C1-C4 alkane 8 is extracted from the unit in a gas state and is sent to the subsequent olefin refining treatment, unreacted components are circulated to the inlet of the microwave catalytic cracking unit 6 in a liquid state, and are mixed with light fraction steam extracted from the crude oil flash unit 3 according to a certain proportion and then enter the microwave catalytic cracking unit 6 for reaction, so that the cyclic utilization of the unreacted components is realized.
Example 1
In consideration of the complexity of crude oil, crude oil is firstly divided into representative components such as naphtha fraction (naphtha) and paraffin of C6-C27 to be subjected to catalytic cracking evaluation under microwave drive one by one, and finally fraction (crop oil) before 440 ℃ of Saite light crude oil is taken as raw material to simulate the real catalytic cracking of crude oil to prepare light olefin.
In this example, the pressure of the feed was controlled at 100kPa and the preheat temperature was 250 ℃ prior to entering the flash unit.
Selecting a plate type flash tower as equipment of a crude oil flash unit, wherein the number of theoretical plates of the flash tower is 5, carrying out isothermal flash operation, controlling the operation pressure to be 10kPa and the operation temperature to be 270 ℃;
the equipment of the microwave catalytic cracking reaction unit adopts a vertical fixed bed reactor, the microwave frequency is 900MHz, and the microwave irradiation intensity is 1000kW/m3The catalyst is 120 meshes of SiC powder loaded with 2 wt.% of carbon, light fraction steam enters from the top of the reactor and flows from top to bottom, and the mass space velocity of the catalytic cracking reaction is kept at 0.4h-1；
The equipment of the product crude separation and unconverted fraction circulating unit is flash tank, and is subjected to isothermal flash at 30 deg.C, and the operation pressure is controlled at 100 kPa.
A0.2 g sample of each crude oil component was catalytically cracked in a batch reactor with 0.5g catalyst within 5min to simulate the process of producing olefins by microwave-driven catalytic cracking of crude oil in a fixed bed mode, and the results are shown in FIGS. 2 to 4.
The results of fig. 2-4 demonstrate that, under suitable microwave irradiation and catalyst action, each of the representative components in the crude oil can be cracked to light olefins with high selectivity in 60s under mild conditions of less than 350 ℃. The selectivity of all the components converted into light olefin under microwave is not lower than 71%, and the once-through yield of the light olefin is not lower than 31%. It is worth noting that the selectivity of light olefin to straight paraffin components is as high as 85% and the corresponding single-pass yield can reach about 69%, thus reflecting the advantage of high efficiency and rapidness in olefin preparation by microwave-driven crude oil catalytic cracking.
Example 2
The representative component (naphtha, the final distillation point of the naphtha is 205 ℃) in the crude oil is used as the feed of the microwave catalytic cracking reaction unit to simulate the catalytic cracking of the light mixed component in the crude oil to prepare the light olefin.
In this example, the pressure of the feed was controlled at 70kPa and the preheat temperature was 200 ℃ prior to entering the flash unit.
Selecting a plate type flash tower as equipment of a crude oil flash unit, wherein the number of theoretical plates of the flash tower is 3, carrying out isothermal flash operation, controlling the operation pressure at 50kPa and the operation temperature at 220 ℃;
the equipment of the microwave catalytic cracking reaction unit adopts a vertical fluidized bed reactor, the microwave frequency is 2.45GHz, and the microwave irradiation intensity is 1500kW/m3The catalyst is 120-mesh SiC powder loaded with 2 wt.% of carbon; the light fraction steam enters from the bottom of the reactor and flows from bottom to top, the catalyst powder is sprayed from the top of the reactor and flows from top to bottom to form counter-current flow with the light fraction steam, and the mass flow ratio of the light fraction steam to the catalyst powder is controlled at 0.4.
The equipment of the product crude separation and unconverted fraction circulating unit is flash tank, and is subjected to isothermal flash at 20 deg.C, and the operation pressure is controlled at 200 kPa.
0.5g of catalyst sample is soaked by 0.2g of mixed component sample, the mixed system is arranged at the bottom of a quartz reaction tube with one end sealed and the inner diameter of 8mm, one open end of the quartz tube is connected with a gas collecting device for collecting cracked gas products, and the amount and the composition of the gas products can be determined through volume measurement and chromatographic analysis. The residence time (i.e., reaction time) was controlled to 10s by controlling the speed of the catalyst loading zone in the quartz tube through the microwave irradiation zone, thereby achieving the purpose of simulating the fluidized bed operation mode, and the results were shown in fig. 5 to 6.
From the results of fig. 5-6, it can be seen that the catalytic material can maintain the catalytic performance well, wherein the total selectivity of olefins from C2 to C4 is maintained above 71%, and the total yield of light olefins calculated by combining the material balance data can be maintained around 57% after the catalyst is recycled for 6 times.
Example 3
All fractions with atmospheric boiling points before 440 ℃ in Saite light crude oil are used as the feed of a microwave catalytic cracking reaction unit to simulate the process of preparing light olefins by the catalytic cracking of real fully mixed fraction crude oil.
In this example, the pressure of the feed was controlled at 130kPa and the preheat temperature was 300 ℃ prior to entering the flash unit.
Selecting a plate flash tower as equipment of a crude oil flash unit, wherein the number of theoretical plates of the flash tower is 5, carrying out isothermal flash operation, controlling the operation pressure to be 3kPa and the operation temperature to be 300 ℃;
the equipment of the microwave catalytic cracking reaction unit adopts a vertical fluidized bed reactor, the microwave frequency is 2.45GHz, and the microwave irradiation intensity is 3000kW/m3The catalyst is 300 meshes of MnOx powder loaded with 0.5 wt.% of carbon; the light fraction steam enters from the bottom of the reactor and flows from bottom to top, the catalyst powder is sprayed from the top of the reactor and flows from top to bottom to form counter-current flow with the light fraction steam, and the mass flow ratio of the light fraction steam to the catalyst powder is controlled at 0.8.
The equipment of the product crude separation and unconverted fraction circulating unit is flash tank, and is subjected to isothermal flash at 30 deg.C, and the operation pressure is controlled at 50 kPa.
0.5g of catalyst sample is soaked by 0.4g of mixed component sample, the mixed system is arranged at the bottom of a quartz reaction tube with one end sealed and the inner diameter of 8mm, one open end of the quartz tube is connected with a gas collecting device for collecting cracked gas products, and the amount and the composition of the gas products can be determined through volume measurement and chromatographic analysis. The simulation achieved fluidized bed operation mode by controlling the residence time 5s by controlling the velocity of the catalyst loading zone in the quartz tube through the microwave irradiation zone, and the results are shown in fig. 7 to 8.
From the results of fig. 7-8, it can be seen that the catalytic material can maintain the catalytic performance well, wherein the total selectivity of olefins from C2 to C4 is maintained above 76%, and the total yield per pass of light olefins calculated by combining the mass balance data can be maintained at 40.6% or above after 5 times of catalyst recycling.
Claims (10)
1. A method for preparing light olefins by microwave-driven crude oil catalytic cracking is characterized by comprising the following steps:
the method comprises the following steps that a crude oil raw material firstly enters a dehydration and metal ion unit, is dehydrated and demetallized, and then is preheated and enters a crude oil flash evaporation unit, wherein the feeding temperature is controlled to be 200-350 ℃, and the pressure is controlled to be 70-150 kPa;
in the crude oil flash unit, crude oil is cut into heavy fraction and light fraction, the heavy fraction is extracted from the bottom of the flash unit, and the light fraction is extracted from the top of the flash unit and then enters the microwave catalytic cracking reaction unit;
in a microwave catalytic cracking reaction unit, the light fraction steam is contacted with a catalyst and heated to 100-350 ℃ under microwave irradiation for catalytic cracking reaction to generate a main product of C2-C4 light olefin and simultaneously generate a certain amount of H as a byproduct2C1-C4 alkane, the mixed gas flow after the microwave catalytic cracking reaction enters a product crude separation and unreacted fraction circulating unit;
in a product crude separation and unreacted fraction recycling unit, the mixed gas flow is cooled and primary separation is realized, wherein C2-C4 light olefins and byproduct H2C1-C4 alkane is extracted from the unit in a gaseous form and sent to the subsequent olefin refining treatment, and unreacted components are recycled to the inlet of the microwave catalytic cracking unit in a liquid form and mixed with light fraction steam extracted from the flash unit according to a certain proportionAnd then the mixture enters a microwave catalytic cracking unit for reaction, so that the cyclic utilization of unreacted components is realized.
2. The method for preparing light olefins by microwave-driven catalytic cracking of crude oil according to claim 1, wherein the equipment of the crude oil flash unit is a plate flash tower, the number of theoretical plates of the flash tower is 1-10, isothermal flash operation is performed, the operating pressure is 1-50 kPa, and the operating temperature is 220-320 ℃.
3. The method for preparing light olefins by microwave-driven crude oil catalytic cracking according to claim 1, wherein the equipment of the microwave catalytic cracking reaction unit adopts a vertical fixed bed reactor, and the microwave frequency is 900 MHz; or the equipment of the microwave catalytic cracking reaction unit adopts a vertical fluidized bed reactor, and the microwave frequency is 2.45 GHz.
4. The method for preparing light olefins by microwave-driven crude oil catalytic cracking as claimed in claim 3, wherein when a fixed bed reactor is adopted, the light fraction vapor enters from the top of the vertical reactor and flows from top to bottom, and the mass space velocity of the catalytic cracking reaction is kept at 0.4-2 h-1The corresponding microwave irradiation intensity in the reactor is controlled to be 5-10000 kW/m3。
5. The method for preparing light olefins by microwave-driven crude oil catalytic cracking as claimed in claim 4, wherein the intensity of microwave irradiation in the reactor is controlled to 50-3000 kW/m3。
6. The method for preparing light olefins by microwave-driven catalytic cracking of crude oil according to claim 3, wherein when a fluidized bed reactor is adopted, the light fraction vapor enters from the bottom of the reactor and flows from bottom to top, the catalyst powder is sprayed from the top of the reactor and flows from top to bottom to form a counter-current flow with the light fraction vapor, and the ratio of the mass flow of the light fraction vapor to the mass flow of the catalyst powder is controlled at 0.1 to2, the retention time is controlled to be 0.1-10 s, and the corresponding microwave irradiation intensity in the reactor is controlled to be 50-20000 kW/m3。
7. The method for preparing light olefins by catalytic cracking of crude oil driven by microwaves as claimed in claim 6, wherein the intensity of the corresponding microwave irradiation in the reactor is controlled to be 100-5000 kW/m3。
8. The method for preparing light olefins by microwave-driven crude oil catalytic cracking according to claim 1, wherein the catalyst adopted by the microwave catalytic cracking unit is activated carbon, carbon black or a supported carbon catalyst, and the carrier of the supported carbon catalyst is ZSM-5 molecular sieve, SiC or ZrO2、Al2O3、MgO、Cr2O3、V2O5And one or more of MnOx, wherein the carbon loading amount in the supported carbon catalyst is controlled to be 0.5-2.5 wt.%.
9. The method for preparing light olefins by microwave-driven crude oil catalytic cracking according to claim 1 or 8, wherein the particle size of the catalyst is controlled within 320-50 meshes.
10. The method for preparing light olefins by microwave-driven catalytic cracking of crude oil according to claim 1, wherein the equipment of the product crude separation and unconverted fraction circulating unit is a flash tank, isothermal flash is performed at 10-40 ℃, and the operating pressure is controlled at 50-500 kPa.
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