CN113004934B - Steam cracking process - Google Patents
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- CN113004934B CN113004934B CN201911330563.6A CN201911330563A CN113004934B CN 113004934 B CN113004934 B CN 113004934B CN 201911330563 A CN201911330563 A CN 201911330563A CN 113004934 B CN113004934 B CN 113004934B
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G9/34—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts
- C10G9/36—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts with heated gases or vapours
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/32—Reaction with silicon compounds, e.g. TEOS, siliconfluoride
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/38—Base treatment
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
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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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the field of steam cracking, in particular to a steam cracking method. The method comprises the following steps: introducing a raw material flow into a tubular cracking device to carry out steam cracking under the conditions of more than 550 ℃ and the presence of steam, wherein the raw material flow comprises cracking raw oil and a modified molecular sieve, and the modified molecular sieve is obtained by amine protection and oil-soluble modification of an original molecular sieve. The method changes the distribution of steam cracking products, improves the yield of main cracking products such as ethylene, propylene and the like, and increases the yield of low-carbon olefin.
Description
Technical Field
The invention relates to the field of steam cracking, in particular to a steam cracking method.
Background
Ethylene and propylene are the most important basic raw materials in petrochemical industry. However, the cracking apparatus has to be faced with the problem that the raw materials become increasingly complex due to the consumption of petroleum resources and the growth of ethylene industry, and the cracking raw materials have been diversified and complicated. For steam cracking processes, the cracking feedstock cost is more than 70% of the total cost, so better utilization of the cracking feedstock is beneficial to improving the overall economic efficiency of the ethylene plant.
However, the existing cracking processes, including steam cracking and catalytic cracking, generally have the problems of easy coking, shutdown, low olefin yield, high energy consumption and the like, so that a steam cracking method for simply and conveniently improving the olefin yield is urgently needed.
Disclosure of Invention
One of the purposes of the invention is to improve the yield of ethylene and propylene in the steam cracking process;
the invention also aims to improve the mixing uniformity of the modified molecular sieve and the cracking raw oil.
The invention provides a steam cracking method, which comprises the following steps: introducing a raw material flow into a tubular cracking device to carry out steam cracking under the conditions of more than 550 ℃ and the presence of steam, wherein the raw material flow comprises cracking raw oil and a modified molecular sieve, and the modified molecular sieve is obtained by amine protection and oil-soluble modification of an original molecular sieve.
The steam cracking method changes the distribution of the steam cracking products, improves the yield of main cracking products such as ethylene, propylene and the like, and increases the yield of low-carbon olefins.
Drawings
FIG. 1 is a schematic diagram of comparative example 1 in which oil-soluble modification was performed.
FIG. 2 is a schematic diagram of amine protection and oil-soluble modification performed in example 1.
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.
The invention provides a steam cracking method, which comprises the following steps: introducing a raw material flow into a tubular cracking device to carry out steam cracking under the conditions of more than 550 ℃ and the presence of steam, wherein the raw material flow comprises cracking raw oil and a modified molecular sieve, and the modified molecular sieve is obtained by amine protection and oil-soluble modification of an original molecular sieve.
According to the invention, the "tubular cracking unit" is a unit commonly used in steam cracking processes.
According to the invention, the steam is introduced into the tubular cracking unit in the form of high-temperature steam.
According to the present invention, preferably, the amine protection comprises first contacting the original molecular sieve with an amine protecting agent at 60-90 ℃ and drying to obtain the amine protected molecular sieve.
Preferably, the amine protectant is ammonia and/or an organic amine; more preferably, the organic amine is selected from at least one of ethylenediamine, methylamine, ethylamine, and propylamine.
Preferably, the molar amount of the amine protective agent is greater than or equal to the molar content of Al in the original molecular sieve. Preferably, the molar ratio of the amine protecting agent to Al in the original molecular sieve is 1.2-2, such as 1.5. The Al mole content in the molecular sieve is determined by the amount of the original molecular sieve and the SiO content of the molecular sieve 2 /Al 2 O 3 Calculated by molar ratio.
Preferably, the oil-soluble modification comprises: reacting the modifier with the amine-protected molecular sieve in the presence of a solvent at 50-90 ℃. The solvent is any commonly used solvent capable of dissolving the modifying agent. For example, an alkane, an alcohol, or the like may be used.
Preferably, the conditions of the reaction include: the temperature is 50-90 deg.C, and the time is 12-72 hr, preferably 60-80 deg.C, and the time is 12-36 hr.
Preferably, the modifier is a silane having a general formula shown in formula (I),
in the formula (I), R 1 Is selected from C 5 -C 12 Alkyl of (C) 5 -C 12 Alkenyl, phenyl, preferably selected from C 5 -C 10 Alkyl of (C) 5 -C 10 Alkenyl, phenyl of (a);
R 2 、R 3 、R 4 are the same or different and are each independently selected from C 1 -C 5 Preferably, each is independently selected from C 1 -C 3 Alkyl group of (1).
Preferably, the modifier is selected from at least one of octyltrimethoxysilane, octyltriethoxysilane, and phenyltriisopropoxysilane.
In a specific embodiment, the modifier is octyl trimethoxy silane, the modifier is dissolved in a proper amount of n-octane and then mixed with a molecular sieve, the obtained mixture is heated to reflux, and after 12-72 hours of reaction, the mixture is filtered and dried at 70-100 ℃ for 2-10 hours.
Preferably, the modifier is used in an amount of 5 to 25 parts by weight, preferably 5 to 15 parts by weight, relative to 100 parts by weight of the original molecular sieve.
Preferably, the mass content of the modified molecular sieve in the feed stream is from 500 to 8000ppm, preferably from 1000 to 5000ppm, more preferably from 1000 to 3000ppm.
According to the present invention, the raw molecular sieve may be a hydrogen type molecular sieve and/or a sodium type molecular sieve commercially available. Preferably, the raw molecular sieve is selected from at least one of a ZSM-5 type molecular sieve, a Y type molecular sieve and a Beta molecular sieve.
Preferably, the SiO of the primary molecular sieve 2 /Al 2 O 3 The molar ratio is from 25 to 500, preferably from 50 to 200.
Preferably, the primary molecular sieve has a crystallite size of no greater than 600nm, preferably from 50 to 500nm, more preferably from 200 to 500nm.
Preferably, the specific surface area of the raw molecular sieve is 350-450m 2 Per g, the micropore area is 300-400m 2 The total pore volume is 0.25-0.3mL/g, and the micropore volume is 0.15-0.2mL/g.
Herein, the raw molecular sieve specific surface area, micropore volume and total pore volume are all measured by the BET nitrogen adsorption method; siO 2 2 /Al 2 O 3 The molar ratio is determined by X-ray fluorescence spectroscopy.
Preferably, the steam cracking conditions include: the temperature is 700 deg.C, preferably 700-900 deg.C, and more preferably 750-860 deg.C.
Preferably, the steam cracking conditions include: the residence time of the feed stream does not exceed 2.5s, preferably 0.1 to 0.5s; the water-oil mass ratio is not more than 3, preferably 0.2-1.
Preferably, the cracking raw oil is at least one selected from diesel oil, aviation kerosene, naphtha, topping oil, raffinate oil and hydrogenation tail oil. More preferably, the distillation range end point of the cracking raw oil is not more than 300 ℃, and preferably 100-300 ℃.
According to the invention, the amine protective agent is firstly combined with the acid centers of the molecular sieve, so that the reaction between the acid centers of the molecular sieve and the modifier is avoided (see the schematic diagram of figure 2), and the acid centers originally combined with the amine protective agent are released again at high temperature in the steam cracking process, thereby increasing the mixing uniformity of the molecular sieve and the cracking raw oil and simultaneously keeping more active centers of the molecular sieve.
The present invention will be described in detail below by way of examples.
The physical properties of the cracking feedstock used in each example are shown in Table 1.
TABLE 1
Comparative example 1
ZSM-5 type commercial ZNP molecular sieve (the grain size of the molecular sieve is 300-500nm, siO) 2 /Al 2 O 3 Molar ratio of 50), physical property analysis is shown in table 2.
(1) Dissolving 10g of octyl trimethoxy silane in a proper amount of n-octane, pouring the mixture into a three-neck flask, mixing the mixture with 100g of ZNP molecular sieve, heating and refluxing for 24 hours, washing, performing suction filtration, and drying a filter cake in an oven at 100 ℃ for 6 hours. And grinding the dried filter cake to obtain the oil-soluble modified molecular sieve (the schematic diagram is shown in figure 1), and marking as the molecular sieve ZSM-5-d.
(2) Molecular sieve ZSM-5-d was thoroughly mixed with cracked feedstock (physical analysis is shown in Table 1) to form a feed stream, wherein the molecular sieve ZSM-5-d had a mass concentration of 2000ppm.
(3) The feed stream was introduced into a cracking furnace tube and steam cracked at a temperature of 840 deg.C, a feed stream residence time of 0.25s, and a water-to-oil mass ratio of 0.5. Meanwhile, cracking raw oil without molecular sieve ZSM-5-d is set to carry out steam cracking under the same conditions to serve as a control experiment. The ethylene and propylene yields are shown in Table 3.
TABLE 2
Comparative example 2
(1) The modified molecular sieve was prepared as follows:
mixing 10g of alumina powder and 235g of tetrapropylammonium hydroxide, placing the mixture in a high-pressure reaction kettle, and reacting at 100-170 ℃ to obtain the quaternary ammonium aluminum source. Adopting hydrothermal crystallization method to make 1290g of silica gel (Na/SiO) 2 The mol ratio of 0.04), 245g of quaternary ammonium aluminum source and water are evenly mixed according to a certain proportion, transferred to a high-pressure crystallization kettle and crystallized for 1 to 3 days at the temperature of between 80 and 180 ℃, and after the crystallization is finished, the ZSM-5 type molecular sieve ZSM-5-1 (the size of the molecular sieve crystal grain is 200nm and SiO is not roasted at high temperature) containing the template agent (tetrapropylammonium hydroxide) is obtained by filtering, separating and drying 2 /Al 2 O 3 A molar ratio of 200); 10g of octyl trimethoxy silane is dissolved in a proper amount of n-octane, poured into a three-neck flask and mixed with 100g of molecular sieve ZSM-5-1, heated and refluxed for 24 hours, washed and filtered. The filter cake was dried at 100 ℃ for 6h. And grinding the dried filter cake to obtain the modified molecular sieve ZSM-5-e.
(2) Molecular sieve ZSM-5-e and cracking raw oil (shown in table 1 for physical analysis) are fully mixed to form a feed stream, wherein the mass concentration of the molecular sieve ZSM-5-e is 2000ppm.
(3) Introducing the raw material flow into a cracking furnace tube, and carrying out steam cracking under the conditions that the temperature is 820 ℃, the retention time of the raw material flow is 0.25s and the mass ratio of water to oil is 0.5. Meanwhile, cracking raw oil without molecular sieve ZSM-5-e is set to carry out steam cracking under the same conditions to serve as a control experiment. The ethylene and propylene yields are shown in Table 3.
Example 1
ZSM-5 type commercial ZNP molecular sieve (the grain size of the molecular sieve is 300-500nm, siO) 2 /Al 2 O 3 Molar ratio of 50), physical property analysis is shown in table 2.
(1) Dispersing a ZNP molecular sieve in a proper amount of deionized water, adding ammonia water according to the silicon-aluminum ratio of the molecular sieve and the weight of the molecular sieve, enabling the molar ratio of ammonia to aluminum to be 1.5, stirring and heating at 80 ℃ for 2 hours, and drying the mixture at 100 ℃ for 8 hours. Grinding the dried amine-protected molecular sieve into powder; oil soluble modification was then carried out as described in comparative example 1 to give a modified molecular sieve (schematic shown in FIG. 2) designated ZSM-5-f.
(2) Molecular sieve ZSM-5-f was thoroughly mixed with cracked feedstock (physical analysis shown in Table 1) to form a feed stream, wherein the concentration of molecular sieve ZSM-5-f was 2000ppm.
(3) Introducing the raw material flow into a cracking furnace tube, and carrying out steam cracking under the conditions that the temperature is 820 ℃, the retention time of the raw material flow is 0.25s and the mass ratio of water to oil is 0.5. Meanwhile, cracking raw oil without molecular sieve ZSM-5-f is subjected to steam cracking under the same conditions to serve as a control experiment. The ethylene and propylene yields are shown in Table 3.
Example 2
A modified molecular sieve was prepared as described in reference to example 1, except that dodecyltrimethoxysilane was used instead of octyltrimethoxysilane, and the rest was the same as in example 1, to finally obtain molecular sieve ZSM-5-g. Then, the steam cracking was carried out by the method described in example 1 using molecular sieve ZSM-5-g, and the yields of ethylene and propylene were as shown in Table 3.
Example 3
A modified molecular sieve was prepared as described in reference to example 1, except that ethyltrimethoxysilane was used in place of octyltrimethoxysilane, and the rest was the same as in example 1, to finally obtain molecular sieve ZSM-5-h. The steam cracking was then carried out using molecular sieve ZSM-5-h as described in example 1, with ethylene and propylene yields as shown in Table 3.
Example 4
A modified molecular sieve was prepared as described in example 1, except that octyltrimethoxysilane was used in an amount of 5g, and the rest was the same as in example 1, to finally obtain molecular sieve ZSM-5-i. The steam cracking was then carried out using molecular sieve ZSM-5-i as described in example 1, with ethylene and propylene yields as shown in Table 3.
TABLE 3
As can be seen from the results in Table 3, compared with the blank control experiment, the modified molecular sieve obtained by sequentially carrying out amine protection and oil-soluble modification on the original molecular sieve is used for carrying out steam cracking on the original molecular sieve, and the yield of propylene and ethylene in the steam cracking product can be effectively improved by using the modified molecular sieve for carrying out steam cracking.
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 (19)
1. A steam cracking process, the process comprising: introducing a raw material flow into a tubular cracking device to carry out steam cracking at the temperature of above 700 ℃ in the presence of steam, wherein the raw material flow comprises cracking raw oil and a modified molecular sieve, and the modified molecular sieve is obtained by amine protection and oil-soluble modification of an original molecular sieve;
the original molecular sieve is selected from at least one of a ZSM-5 type molecular sieve, a Y type molecular sieve and a Beta molecular sieve;
the amine protection comprises the steps of carrying out first contact on an original molecular sieve and an amine protective agent at the temperature of 60-90 ℃, and drying to obtain an amine-protected molecular sieve; the amine protective agent is ammonia water;
the oil-soluble modification comprises: in the presence of a solvent, reacting a modifier with an amine-protected molecular sieve at 50-90 ℃;
the modifier is silane with a general formula shown in a formula (I),
in the formula (I), R 1 Is selected from C 5 -C 12 Alkyl of (C) 5 -C 12 Alkenyl, phenyl of (a);
R 2 、R 3 、R 4 are the same or different and are each independently selected from C 1 -C 5 Alkyl group of (1).
2. The method of claim 1, wherein the conditions of the oil-soluble modification reaction comprise: the temperature is 60-80 ℃ and the time is 12-72h.
3. The method according to claim 1, wherein, in formula (I), R 1 Is selected from C 5 -C 10 Alkyl of (C) 5 -C 10 Alkenyl, phenyl of (i);
R 2 、R 3 、R 4 each independently selected from C 1 -C 3 Alkyl group of (1).
4. The process of claim 1, wherein the modifier is selected from octyltrimethoxysilane, phenyltrimethoxysilane, octyltriethoxysilane, and phenyltriisopropoxysilane.
5. The method of claim 1, wherein the modifier is used in an amount of 5 to 25 parts by weight, relative to 100 parts by weight of the original molecular sieve.
6. The method of claim 5, wherein the modifier is used in an amount of 5 to 15 parts by weight, relative to 100 parts by weight of the original molecular sieve.
7. The process of any of claims 1-6, wherein the feed stream has a mass content of the modified molecular sieve of 500 to 8000ppm.
8. The process of claim 7, wherein the feed stream comprises the modified molecular sieve in an amount of from 1000 to 5000ppm by mass.
9. The process of claim 8, wherein the feed stream comprises about 1000 ppm to about 3000ppm by weight of the modified molecular sieve.
10. The method of any one of claims 1-6, wherein the SiO of the raw molecular sieve 2 /Al 2 O 3 The molar ratio is 25-500;
and/or the crystal grain size of the original molecular sieve is not more than 600nm.
11. The method of claim 10, wherein the SiO of the raw molecular sieve 2 /Al 2 O 3 The molar ratio is 50-200;
and/or the crystal grain size of the original molecular sieve is 50-500nm.
12. The method of claim 11, wherein the raw molecular sieve has a crystallite size of 200 to 500nm.
13. The method of any one of claims 1-6, wherein the steam cracking conditions comprise: the temperature is 700-900 ℃.
14. The method of claim 13, wherein the steam cracking conditions comprise: the temperature is 750-860 ℃.
15. The method of any of claims 1-6, wherein the conditions of the steam cracking comprise: the retention time of the raw material flow does not exceed 2.5s, and the water-oil mass ratio does not exceed 3.
16. The method of claim 15, wherein the steam cracking conditions comprise: the residence time of the raw material flow is 0.1-0.5s, and the water-oil mass ratio is 0.2-1.
17. The process according to any one of claims 1-6, wherein the pyrolysis feedstock oil is selected from at least one of diesel, jet fuel, naphtha, topped oil, raffinate oil, and hydrotreated tail oil.
18. The process of claim 17, wherein the distillation range end point of the cracked feedstock oil is no greater than 300 ℃.
19. The process according to claim 18, wherein the distillation range end point of the cracked feedstock oil is from 100 ℃ to 300 ℃.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5371312A (en) * | 1993-04-05 | 1994-12-06 | Mobil Oil Corp. | Shape selective hydrocarbon conversions over modified catalyst |
| US6284696B1 (en) * | 1996-06-07 | 2001-09-04 | Asahi Kasei Kogyo Kabushiki Kaisha | Mesopore molecular sieve and process for the production thereof |
| CN101619011A (en) * | 2008-06-30 | 2010-01-06 | 中国石油化工股份有限公司 | Method for producing ethylene and propylene by catalytic cracking |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5371312A (en) * | 1993-04-05 | 1994-12-06 | Mobil Oil Corp. | Shape selective hydrocarbon conversions over modified catalyst |
| US6284696B1 (en) * | 1996-06-07 | 2001-09-04 | Asahi Kasei Kogyo Kabushiki Kaisha | Mesopore molecular sieve and process for the production thereof |
| CN101619011A (en) * | 2008-06-30 | 2010-01-06 | 中国石油化工股份有限公司 | Method for producing ethylene and propylene by catalytic cracking |
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