EP0262049B1 - Process for up-grading steam-cracking products - Google Patents
Process for up-grading steam-cracking products Download PDFInfo
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- EP0262049B1 EP0262049B1 EP19870402135 EP87402135A EP0262049B1 EP 0262049 B1 EP0262049 B1 EP 0262049B1 EP 19870402135 EP19870402135 EP 19870402135 EP 87402135 A EP87402135 A EP 87402135A EP 0262049 B1 EP0262049 B1 EP 0262049B1
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- European Patent Office
- Prior art keywords
- steam
- zeolite
- cracking
- zsm
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000004230 steam cracking Methods 0.000 title claims description 38
- 238000000034 method Methods 0.000 title claims description 28
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 31
- 239000010457 zeolite Substances 0.000 claims description 31
- 229910021536 Zeolite Inorganic materials 0.000 claims description 30
- 239000003054 catalyst Substances 0.000 claims description 28
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 22
- 239000000047 product Substances 0.000 claims description 20
- 229930195733 hydrocarbon Natural products 0.000 claims description 16
- 150000002430 hydrocarbons Chemical class 0.000 claims description 16
- 230000003197 catalytic effect Effects 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 239000010425 asbestos Substances 0.000 claims description 10
- 229910052593 corundum Inorganic materials 0.000 claims description 10
- 229910052895 riebeckite Inorganic materials 0.000 claims description 10
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000007789 gas Substances 0.000 description 10
- 239000004215 Carbon black (E152) Substances 0.000 description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 9
- 239000005977 Ethylene Substances 0.000 description 9
- 150000001336 alkenes Chemical class 0.000 description 9
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 230000004048 modification Effects 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000001965 increasing effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 150000003738 xylenes Chemical class 0.000 description 4
- SQNZJJAZBFDUTD-UHFFFAOYSA-N durene Chemical compound CC1=CC(C)=C(C)C=C1C SQNZJJAZBFDUTD-UHFFFAOYSA-N 0.000 description 3
- 239000008246 gaseous mixture Substances 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000007792 gaseous phase Substances 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- PRAKJMSDJKAYCZ-UHFFFAOYSA-N squalane Chemical compound CC(C)CCCC(C)CCCC(C)CCCCC(C)CCCC(C)CCCC(C)C PRAKJMSDJKAYCZ-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000011021 bench scale process Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- -1 ethylene, propylene, butenes Chemical class 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- JXTPJDDICSTXJX-UHFFFAOYSA-N n-Triacontane Natural products CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC JXTPJDDICSTXJX-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 229940032094 squalane Drugs 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Images
Classifications
-
- 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
- C10G63/00—Treatment of naphtha by at least one reforming process and at least one other conversion process
- C10G63/02—Treatment of naphtha by at least one reforming process and at least one other conversion process plural serial stages only
- C10G63/04—Treatment of naphtha by at least one reforming process and at least one other conversion process plural serial stages only including at least one cracking step
-
- 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
- C10G35/00—Reforming naphtha
- C10G35/04—Catalytic reforming
- C10G35/06—Catalytic reforming characterised by the catalyst used
- C10G35/095—Catalytic reforming characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
Definitions
- Steam-cracking is one of the most widely used basic petrochemical processes. It is used by industries to produce light olefins such as ethylene, propylene, butenes and butadiene and it is also relied upon for the production of aromatics such as benzene, toluene and xylenes.
- steam-cracking comprises a step in which the hydrocarbon mixture to be transformed is mixed with steam and submitted to elevated temperatures in a tubular reactor.
- the different resulting products, gaseous and liquid hydrocarbons are then collected and separated.
- product distribution depends on the nature of the initial hydrocarbon mixture as well as experimental conditions.
- C2-C4 light olefins as well as benzene, toluene, ethylbenzene and xylenes have the highest commercial values and since enormous quantities are processes throughout the world, even small yield improvements lead to substantial profit increases.
- ZSM-5 zeolite catalysts have drawn considerable attention because of their ability to increase selectivity in a variety of industrial processes such as xylene isomerization, toluene disproportionation, aromatic alkylation, methanol conversion and conversion of synthesis gas to ethane.
- US 4 472 535 discloses a method of converting a synthesis gas mixture comprising hydrogen and carbon monoxide to a hydrocarbon product, with improved selectivity for the production of ethane, which comprises contacting the synthesis gas under conversion conditions with a conversion catalyst comprising a crystalline zeolite component having acidic functionality and a metal component impregnated into the zeolite from a liquid ammonia solution wherein said metal component comprises a metal or metals which are an effective catalyst for the conversion of synthesis gas to methanol.
- modifications of the catalyst can also lead to highly efficient production of light olefins resulting from methanol conversion.
- modified zeolite catalysts have the possibilities to present very interesting properties for enhancing yields in petrochemical reactions.
- the present invention relates to a process for up-grading products resulting from the steam-cracking of hydrocarbons which comprises bringing the steam-cracking reaction products in contact with a multifunctional Zn-ZSM-5 zeolite/Cr2O3/Al2O3 catalyst comprising of a mixture of from 2.5 to 7.5% wt of Cr2O3, 5 to 17.5% wt of Al2O3 and 75 to 85% wt of a Zn-ZSM-5 zeolite or a Zn-ZSM-5 zeolite/asbestos.
- a multifunctional Zn-ZSM-5 zeolite/Cr2O3/Al2O3 catalyst comprising of a mixture of from 2.5 to 7.5% wt of Cr2O3, 5 to 17.5% wt of Al2O3 and 75 to 85% wt of a Zn-ZSM-5 zeolite or a Zn-ZSM-5 zeolite/asbestos.
- the main feature of the present invention resides in the presence of a catalytic reactor at the outlet of the steam-cracking reactor.
- This catalytic reactor contains a multifunctional catalyst which comprises a zeolite of the ZSM-5 type coupled with metallic oxides.
- These oxides can either be coupled to the zeolite by being directly deposited on the zeolite or mechanically mixed with the zeolite.
- the metallic oxides can be selected from oxides such as Cr2O3, Al2O3, or from any metallic oxide having a hydrogenating/dehydrogenating function.
- catalytic reactor used in the present invention was a fixed-bed reactor, it will be understood that any suitable design commonly used for catalytic reactions could have been chosen.
- the starting hydro-carbon material 2 is first mixed with a stripping gas 4. It is to be noted, however, that the use of a stripping gas is optional. In the context of the actual experiments, a stripping gas was used only for convenience.
- the resulting mixture is then forwarded to a vaporizer-mixer 6, in which steam is injected by means of an infusion pump 8.
- the gaseous mixture thus obtained enters a steam-cracking tubular reactor 10 heated at a temperature ranging between 760° and 860°C.
- products coming out of the steam-cracking tubular reactor 10 are sent into a catalytic reactor 12 heated at a temperature ranging between 450° and 550°C.
- the resulting products are then cooled by a series of condensers 14 (water-cooling condensers and ice bath).
- the liquid and gaseous phases are separated.
- the liquids are first collected in a liquid-collector cylinder 16 while the gases flow through the liquid-collector cylinder to be collected for on line analysis in a dynamic sampler cylinder 18 located at a higher position than the liquid collector cylinder.
- Propane is the starting hydrocarbon material on which the steam-cracking process was performed. It was introduced into the system at a flow rate of 45 ml/min. or 4.95 g/hour. It was first mixed with helium acting as a stripping gas. After having been flown through the vaporizer-mixer, in which steam was injected at a rate of 1.7 g/hour, the gaseous mixture was then sent into the steam-cracking reactor whose internal temperature had been set to 780°C at atmospheric pressure. The residence time of the starting material in the steam-cracking reactor was approximately 1 second.
- the resulting product was then separated into its liquid and the gaseous phases.
- the liquid fraction was analyzed by GC using a capillary column (length: 50 m, PONA® type, fused silica coated with a cross-linked polymer).
- the gases were analyzed on line by gas chromatography.
- a column having a length of 3.5 m packed with Chromosorb® P coated with 20% by weight of Squalane® was used for the analysis.
- the GC used was a dual FID Hewlett-Packard Model 5790 equipped with a 3392A Model integrator. Results are shown in Table 1.
- Example 1 The same procedure as in Example 1 was repeated the only modification being the internal temperature of the steam-cracking reactor which was set at 800°C. Results are shown in Table 1.
- Example 5 The same procedure as in Example 1 was repeated the only modification being the internal temperature of the steam-cracking reactor which was set at 835°C. Results are shown in Table 5.
- propane was chosen as the starting hydrocarbon material. It was mixed with helium and flown through the vaporizer-mixer. The gaseous mixture was then forwarded through the steam-cracking reactor whose internal temperature had been set to 780°C. The resulting products were then sent to the catalytic reactor which had been previously embedded with 4 g of a Zn-Mn-ZSM-5 zeolite which was prepared according to the procedure described in Can. Pat. Appl. S.N. 471,463 (US-A-4 615 995). The temperature of the catalytic reactor had been previously set at 500°C, with a pressure of 1 atmosphere and a W.H.S.V. (weight hourly space velocity) of 1 h ⁇ 1. The final products were analyzed using the techniques discussed in Example 1. Results are shown in Table 2.
- Example 2 The same procedure as in Example 4 was repeated, the only modification being the internal temperature of the steam-cracking reactor which was set at 800°C. Results are shown in Table 2.
- Example 4 The same procedure as in Example 4 was repeated, except for the following modifications: the catalytic reactor was embedded with 4 g of a Zn-Mn-ZSM-5 zeolite/asbestos catalyst prepared according to the procedure described in Can. Pat. Appl. S.N. 471,463 (US-A- 4 615 995). Results are shown in Table 3.
- Example 6 The same procedure as in Example 6 was repeated, the only modification being the internal temperature of the steam-cracking reactor which was set at 800°C. Results are shown in Table 3.
- Example 4 The same procedure as in Example 4 was repeated, except for the following modification: the catalytic reactor was embedded with a Zn-ZSM-5 zeolite/ asbestos/Cr2O3/Al2O3 catalyst.
- the Zn-ZSM-5 zeolite/ asbestos catalyst was prepared according to the method described in Can. Pat. Appl. S.N. 471,463. Then, 4.5 g of the Zn-ZSM-5 zeolite/asbestos catalyst obtained were wet with a solution prepared from 0.3 g of Cr2O3 and 0.4 g of sodium aluminate dissolved in 5 ml of distilled water. The resulting multifunctional catalyst was dried at 120°C for 12 hours and actuated at 500°C for another 12 hour period. Finally, the catalyst was reduced in hydrogen at 350°C for at least 1 hour. Results are shown in Table 4.
- Example 8 The same procedure as in Example 8 was repeated, the only modification being the internal temperature of the steam-cracking reactor which was set at 800°C. Results were shown in Table 4.
- Example 3 a run without catalyst was performed at 835°C. This temperature was fairly close to temperatures used in industrial steam-cracking facilities using propane as a starting hydrocarbon material.
- the product distribution of such a run is compared to the run performed in presence of the Zn-ZSM-5 zeolite/asbestos/Cr2O3/Al2O3 catalyst and with the steam-cracking reactor temperature set at 800°C, as described in Example 9, it can be seen, as it is shown in Table 5, that in the presence of the multifunctional catalyst and with a much lower steam-cracking temperature, higher yields in ethylene and propylene were obtained.
- the propylene yield was nearly doubled (due mainly to a lower steam-cracking temperature) and the ethylene yield was increased by 5 wt percentage points while methane formation was significantly lower.
- the liquid yield was much lower for the run performed at a lower steam-cracking temperature in the presence of the multifunctional catalyst.
- the BTX aromatics benzene, toluene, ethylbenzene and xylenes
- the total "ethylene + propylene" yield can be increased by 10 wt percentage points and the ethylene/propylene wt ratio can be decreased to a very large extent (see Table 5).
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- Oil, Petroleum & Natural Gas (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Description
- Steam-cracking is one of the most widely used basic petrochemical processes. It is used by industries to produce light olefins such as ethylene, propylene, butenes and butadiene and it is also relied upon for the production of aromatics such as benzene, toluene and xylenes.
- Basically, steam-cracking comprises a step in which the hydrocarbon mixture to be transformed is mixed with steam and submitted to elevated temperatures in a tubular reactor. The different resulting products, gaseous and liquid hydrocarbons are then collected and separated. Thus, product distribution depends on the nature of the initial hydrocarbon mixture as well as experimental conditions.
- Among the products obtained, C₂-C₄ light olefins, as well as benzene, toluene, ethylbenzene and xylenes have the highest commercial values and since enormous quantities are processes throughout the world, even small yield improvements lead to substantial profit increases.
- In recent years, ZSM-5 zeolite catalysts have drawn considerable attention because of their ability to increase selectivity in a variety of industrial processes such as xylene isomerization, toluene disproportionation, aromatic alkylation, methanol conversion and conversion of synthesis gas to ethane.
- Thus US 4 472 535 discloses a method of converting a synthesis gas mixture comprising hydrogen and carbon monoxide to a hydrocarbon product, with improved selectivity for the production of ethane, which comprises contacting the synthesis gas under conversion conditions with a conversion catalyst comprising a crystalline zeolite component having acidic functionality and a metal component impregnated into the zeolite from a liquid ammonia solution wherein said metal component comprises a metal or metals which are an effective catalyst for the conversion of synthesis gas to methanol.
- It has been shown that the zeolite's selectivity properties are the result of its tridimensional channel network and of the different pore sizes of its structure.
- One of the most interesting areas where ZSM-5 zeolites have shown substantial catalytic activity is in the process in which methanol is converted into hydrocarbons. Thus, by using appropriate reaction conditions, very high yields in C₅-C₁₁ gasoline hydrocarbons can be obtained. However, this reaction presents the drawback of producing small quantities of durene, an undesirable reaction product.
- Furthermore, modifications of the catalyst can also lead to highly efficient production of light olefins resulting from methanol conversion.
- Thus, it can be seen that modified zeolite catalysts have the possibilities to present very interesting properties for enhancing yields in petrochemical reactions.
- Therefore, since steam-cracking is one of the most widespread petrochemical processes, it would be highly desirable to provide means for increasing production of the most valuable reaction products.
- The present invention relates to a process for up-grading products resulting from the steam-cracking of hydrocarbons which comprises bringing the steam-cracking reaction products in contact with a multifunctional Zn-ZSM-5 zeolite/Cr₂O₃/Al₂O₃ catalyst comprising of a mixture of from 2.5 to 7.5% wt of Cr₂O₃, 5 to 17.5% wt of Al₂O₃ and 75 to 85% wt of a Zn-ZSM-5 zeolite or a Zn-ZSM-5 zeolite/asbestos. Such a process allows for significant yield increases in C₂-C₄ olefins. Furthermore, the commonly obtained pyrolysis oil is up-graded to a high grade gasoline, rich in mono-aromatics and free from undesirable durenes and long aliphatic chains.
- The main feature of the present invention resides in the presence of a catalytic reactor at the outlet of the steam-cracking reactor. This catalytic reactor contains a multifunctional catalyst which comprises a zeolite of the ZSM-5 type coupled with metallic oxides.
- These oxides can either be coupled to the zeolite by being directly deposited on the zeolite or mechanically mixed with the zeolite.
- The metallic oxides can be selected from oxides such as Cr₂O₃, Al₂O₃, or from any metallic oxide having a hydrogenating/dehydrogenating function.
- In the case of the Cr₂O₃/Al₂O₃ proportions of Cr₂O₃ ranging between 2.5 and 7.5% wt, proportions of Al₂O₃ ranging between 5 and 17.5% wt and proportions of the zeolite catalyst ranging between 75 and 85% wt can be used.
- Although the catalytic reactor used in the present invention was a fixed-bed reactor, it will be understood that any suitable design commonly used for catalytic reactions could have been chosen.
- In the drawings:
- Figure 1 represents a schematic drawing of the bench scale setting for the catalytic up-grading of products resulting from the steam-cracking of hydrocarbons.
- Figure 2 represents a comparison between the amounts of C₂-C₄ olefins obtained by steam-cracking alone and by steam-cracking along with various zeolite catalysts.
- Figure 3 represents a comparison between the amounts of ethylene obtained by steam-cracking alone and by steam-cracking along with various zeolite catalysts.
- Referring now to Figure 1, the starting hydro-
carbon material 2 is first mixed with a stripping gas 4. It is to be noted, however, that the use of a stripping gas is optional. In the context of the actual experiments, a stripping gas was used only for convenience. - The resulting mixture is then forwarded to a vaporizer-
mixer 6, in which steam is injected by means of aninfusion pump 8. The gaseous mixture thus obtained enters a steam-crackingtubular reactor 10 heated at a temperature ranging between 760° and 860°C. In a further step, products coming out of the steam-crackingtubular reactor 10 are sent into acatalytic reactor 12 heated at a temperature ranging between 450° and 550°C. The resulting products are then cooled by a series of condensers 14 (water-cooling condensers and ice bath). Immediately following the cooling step, the liquid and gaseous phases are separated. The liquids are first collected in a liquid-collector cylinder 16 while the gases flow through the liquid-collector cylinder to be collected for on line analysis in adynamic sampler cylinder 18 located at a higher position than the liquid collector cylinder. - The present invention will be more readily understood by referring to the following examples which are given to illustrate rather than limit the scope of the invention.
- Propane is the starting hydrocarbon material on which the steam-cracking process was performed. It was introduced into the system at a flow rate of 45 ml/min. or 4.95 g/hour. It was first mixed with helium acting as a stripping gas. After having been flown through the vaporizer-mixer, in which steam was injected at a rate of 1.7 g/hour, the gaseous mixture was then sent into the steam-cracking reactor whose internal temperature had been set to 780°C at atmospheric pressure. The residence time of the starting material in the steam-cracking reactor was approximately 1 second.
- The resulting product was then separated into its liquid and the gaseous phases. The liquid fraction was analyzed by GC using a capillary column (length: 50 m, PONA® type, fused silica coated with a cross-linked polymer). The gases were analyzed on line by gas chromatography. A column having a length of 3.5 m packed with Chromosorb® P coated with 20% by weight of Squalane® was used for the analysis. The GC used was a dual FID Hewlett-Packard Model 5790 equipped with a 3392A Model integrator. Results are shown in Table 1.
- The same procedure as in Example 1 was repeated the only modification being the internal temperature of the steam-cracking reactor which was set at 800°C. Results are shown in Table 1.
- The same procedure as in Example 1 was repeated the only modification being the internal temperature of the steam-cracking reactor which was set at 835°C. Results are shown in Table 5.
- As in Example 1 propane was chosen as the starting hydrocarbon material. It was mixed with helium and flown through the vaporizer-mixer. The gaseous mixture was then forwarded through the steam-cracking reactor whose internal temperature had been set to 780°C. The resulting products were then sent to the catalytic reactor which had been previously embedded with 4 g of a Zn-Mn-ZSM-5 zeolite which was prepared according to the procedure described in Can. Pat. Appl. S.N. 471,463 (US-A-4 615 995). The temperature of the catalytic reactor had been previously set at 500°C, with a pressure of 1 atmosphere and a W.H.S.V. (weight hourly space velocity) of 1 h‾¹. The final products were analyzed using the techniques discussed in Example 1. Results are shown in Table 2.
- The same procedure as in Example 4 was repeated, the only modification being the internal temperature of the steam-cracking reactor which was set at 800°C. Results are shown in Table 2.
- The same procedure as in Example 4 was repeated, except for the following modifications: the catalytic reactor was embedded with 4 g of a Zn-Mn-ZSM-5 zeolite/asbestos catalyst prepared according to the procedure described in Can. Pat. Appl. S.N. 471,463 (US-A- 4 615 995). Results are shown in Table 3.
- The same procedure as in Example 6 was repeated, the only modification being the internal temperature of the steam-cracking reactor which was set at 800°C. Results are shown in Table 3.
- The same procedure as in Example 4 was repeated, except for the following modification: the catalytic reactor was embedded with a Zn-ZSM-5 zeolite/ asbestos/Cr₂O₃/Al₂O₃ catalyst. The Zn-ZSM-5 zeolite/ asbestos catalyst was prepared according to the method described in Can. Pat. Appl. S.N. 471,463. Then, 4.5 g of the Zn-ZSM-5 zeolite/asbestos catalyst obtained were wet with a solution prepared from 0.3 g of Cr₂O₃ and 0.4 g of sodium aluminate dissolved in 5 ml of distilled water. The resulting multifunctional catalyst was dried at 120°C for 12 hours and actuated at 500°C for another 12 hour period. Finally, the catalyst was reduced in hydrogen at 350°C for at least 1 hour. Results are shown in Table 4.
- The same procedure as in Example 8 was repeated, the only modification being the internal temperature of the steam-cracking reactor which was set at 800°C. Results were shown in Table 4.
- When studying the results obtained from the various examples, it is to be noted that in the steam-cracking process alone (Table 1) significant increases in highly valuable compounds such as ethylene, benzene and toluene are observed when the internal temperature of the reactor is increased from 780° to 800°C. The amount of less valuable products such as methane is higher at 800°C but this increase is compensated by a decrease in C₂-C₄ paraffins.
- As for the aromatic content, there is a dramatic decrease in less valuable C₅-C₁₁ aliphatics, resulting in the obtention of more interesting products such as benzene, xylenes and toluene. In examples 4 to 7, Zn-Mn-ZSM-5 zeolite and Zn-Mn-ZSM-5 zeolite/asbestos, two known catalysts were used to form the catalytic bed. As it can be seen in Tables 2 and 3, and in Figures 2 and 3, inferior results were obtained when compared to steam-cracking alone as far as the olefin content is concerned, regardless of the temperature at which the reactions were performed.
- As for the aromatic content, better results were obtained, but these results are at the best sufficient and no more, to compensate the quality loss on the side of the olefin production, especially, as far as ethylene is concerned, since ethylene is the most valuable steam-cracking product.
- Thus, in the light of these results, one could tend to be led away from using zeolite catalysts as means to improve steam-cracking processes.
- In Examples 8 and 9, the results obtained by using a multifunctional catalyst point out better results in both olefin and aromatic productions. Thus, it has been discovered as it can be seen in Figures 2 and 3, that the use of metal oxides co-catalyst coupled with a zeolite type catalyst unexpectedly increases the amounts of valuable steam-cracking products. In fact, the total amount of C₂-C₄ olefins and especially ethylene obtained by using the multifunctional catalyst after a steam-cracking reaction of 780° (55.8% wt) is even superior to the amount obtained when performing the steam-cracking reaction alone at 800° (47.1 wt).
- Moreover as described in Example 3, a run without catalyst was performed at 835°C. This temperature was fairly close to temperatures used in industrial steam-cracking facilities using propane as a starting hydrocarbon material. When the product distribution of such a run is compared to the run performed in presence of the Zn-ZSM-5 zeolite/asbestos/Cr₂O₃/Al₂O₃ catalyst and with the steam-cracking reactor temperature set at 800°C, as described in Example 9, it can be seen, as it is shown in Table 5, that in the presence of the multifunctional catalyst and with a much lower steam-cracking temperature, higher yields in ethylene and propylene were obtained. The propylene yield was nearly doubled (due mainly to a lower steam-cracking temperature) and the ethylene yield was increased by 5 wt percentage points while methane formation was significantly lower.
- Furthermore, the liquid yield was much lower for the run performed at a lower steam-cracking temperature in the presence of the multifunctional catalyst. However, the BTX aromatics (benzene, toluene, ethylbenzene and xylenes) content in the liquid hydrocarbon products was much higher and there was no formation of undesirable hydrocarbons.
- Thus, by performing the steam-cracking of propane at a lower temperature and by using a multifunctional catalyst, the total "ethylene + propylene" yield can be increased by 10 wt percentage points and the ethylene/propylene wt ratio can be decreased to a very large extent (see Table 5).
- From an industrial viewpoint, this would represent a real advantage since the present market trends are for a lower demand in ethylene and an increasing demand in propylene.
- It will be appreciated that even though yields increase in valuable products ranging from 5 to 10% wt do not seem to be of significant importance, because of the enormous amounts of hydrocarbon material refined every day throughout the world, even a 0.5% wt yield increase represents millions of dollars of profits for petrochemical industries. Therefore, it is submitted that every invention increasing production yields in the petrochemical conversion processes has tremendous commercial values for these industries.
Claims (5)
- A process for up-grading products resulting from the steam-cracking of hydrocarbons which comprises bringing the steam-cracking reaction products in contact with a catalyst comprising a mixture of from 2.5 to 7.5% wt of Cr₂O₃, 5 to 17.5% wt of Al₂O₃ and 75 to 85% wt of a Zn-ZSM-5 zeolite or a Zn-ZSM-5 zeolite/asbestos and recovering the desired products.
- The process of Claim 1, wherein Cr₂O₃ and Al₂O₃ are directly deposited on the Zn-ZSM-5 zeolite or the Zn-ZSM-5 zeolite/asbestos.
- The process of Claim 1, wherein Cr₂O₃ and Al₂O₃ are mechanically mixed with the Zn-ZSM-5 zeolite or the Zn-ZSM-5 zeolite/asbestos.
- The process of Claim 1, wherein the catalyst is packed in a tubular reactor.
- The process of Claim 4, wherein the catalytic tubular reactor temperature is maintained between 400° and 600°C.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA000519081A CA1270240A (en) | 1986-09-25 | 1986-09-25 | Process for up-grading steam-cracking products |
CA519081 | 1986-09-25 |
Publications (3)
Publication Number | Publication Date |
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EP0262049A2 EP0262049A2 (en) | 1988-03-30 |
EP0262049A3 EP0262049A3 (en) | 1989-03-22 |
EP0262049B1 true EP0262049B1 (en) | 1992-03-11 |
Family
ID=4134019
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP19870402135 Expired EP0262049B1 (en) | 1986-09-25 | 1987-09-24 | Process for up-grading steam-cracking products |
Country Status (4)
Country | Link |
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EP (1) | EP0262049B1 (en) |
JP (1) | JPS6397233A (en) |
CA (1) | CA1270240A (en) |
DE (1) | DE3777305D1 (en) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0275930B1 (en) * | 1987-01-23 | 1992-01-02 | Mobil Oil Corporation | Upgrading diene-containing hydrocarbons |
DE69016904T2 (en) * | 1989-09-26 | 1995-07-06 | Shell Int Research | Process for improving a feed containing sulfur. |
GB9218346D0 (en) * | 1992-08-28 | 1992-10-14 | Bp Chem Int Ltd | Process |
US6033555A (en) * | 1997-06-10 | 2000-03-07 | Exxon Chemical Patents Inc. | Sequential catalytic and thermal cracking for enhanced ethylene yield |
US7098162B2 (en) * | 2000-07-31 | 2006-08-29 | Valorbec Societe En Commandite | Catalysts for deep catalytic cracking of petroleum naphthas and other hydrocarbon feedstocks for the selective production of light olefins and method of making thereof |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4097367A (en) * | 1977-07-25 | 1978-06-27 | Mobil Oil Corporation | Conversion of olefinic naphtha |
US4188336A (en) * | 1977-08-18 | 1980-02-12 | Mobil Oil Corporation | Conversion of synthesis gas to aromatic hydrocarbons |
US4472535A (en) * | 1982-11-22 | 1984-09-18 | Mobil Oil Corporation | Conversion of synthesis gas to ethane |
DE3473611D1 (en) * | 1983-07-14 | 1988-09-29 | Shell Int Research | Process for upgrading a gasoline |
US4615995A (en) * | 1985-01-03 | 1986-10-07 | The Asbestos Institute | Zeolite catalysts |
-
1986
- 1986-09-25 CA CA000519081A patent/CA1270240A/en not_active Expired - Fee Related
-
1987
- 1987-09-24 EP EP19870402135 patent/EP0262049B1/en not_active Expired
- 1987-09-24 DE DE8787402135T patent/DE3777305D1/en not_active Expired - Fee Related
- 1987-09-24 JP JP23990287A patent/JPS6397233A/en active Pending
Also Published As
Publication number | Publication date |
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EP0262049A3 (en) | 1989-03-22 |
DE3777305D1 (en) | 1992-04-16 |
JPS6397233A (en) | 1988-04-27 |
CA1270240A (en) | 1990-06-12 |
EP0262049A2 (en) | 1988-03-30 |
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