WO2017003014A1 - Procédé pour successivement faire réagir-régénérer et préparer une oléfine de type fluide après prétraitement avec un gaz réducteur - Google Patents
Procédé pour successivement faire réagir-régénérer et préparer une oléfine de type fluide après prétraitement avec un gaz réducteur Download PDFInfo
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- WO2017003014A1 WO2017003014A1 PCT/KR2015/008671 KR2015008671W WO2017003014A1 WO 2017003014 A1 WO2017003014 A1 WO 2017003014A1 KR 2015008671 W KR2015008671 W KR 2015008671W WO 2017003014 A1 WO2017003014 A1 WO 2017003014A1
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- catalyst
- hydrocarbon
- olefin
- reducing gas
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- 150000001336 alkenes Chemical class 0.000 title claims abstract description 128
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 238000000034 method Methods 0.000 title claims abstract description 44
- 239000003054 catalyst Substances 0.000 claims abstract description 237
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 129
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 128
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 117
- 238000006243 chemical reaction Methods 0.000 claims abstract description 91
- 239000006227 byproduct Substances 0.000 claims abstract description 25
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- 230000001172 regenerating effect Effects 0.000 claims abstract description 13
- 239000007789 gas Substances 0.000 claims description 96
- 238000004519 manufacturing process Methods 0.000 claims description 40
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 19
- 239000001301 oxygen Substances 0.000 claims description 19
- 229910052760 oxygen Inorganic materials 0.000 claims description 19
- 238000000926 separation method Methods 0.000 claims description 19
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 16
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 14
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 14
- 238000011069 regeneration method Methods 0.000 claims description 13
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 10
- 239000005977 Ethylene Substances 0.000 claims description 10
- 238000004064 recycling Methods 0.000 claims description 10
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 150000001335 aliphatic alkanes Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 230000003134 recirculating effect Effects 0.000 abstract 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 30
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 16
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 16
- 239000001294 propane Substances 0.000 description 15
- 238000006356 dehydrogenation reaction Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 230000007423 decrease Effects 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 150000002431 hydrogen Chemical class 0.000 description 7
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 3
- 229910000423 chromium oxide Inorganic materials 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/20—Use of additives, e.g. for stabilisation
-
- 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
- Y02P20/584—Recycling of catalysts
Definitions
- the present invention relates to a process for continuous reaction-regeneration and flow olefins after reducing gas pretreatment.
- Olefins such as ethylene and propylene are widely used in the petrochemical industry. Generally these olefins are obtained in the pyrolysis process of naphtha. However, the petrochemical industry requires higher amounts of olefins, so olefins are also produced through dehydrogenation processes using catalysts of lower hydrocarbons.
- Catalytic catalytic dehydrogenation processes for the production of olefins utilize various types of lower hydrocarbon compounds as raw materials and show excellent olefin production yields.
- the hydrocarbon is in contact with the catalyst, even though the olefin yield is high, the numerical value decreases with time, and thus there is a problem in that the conversion rate of the hydrocarbon and the yield of the olefin as a whole decrease.
- a circulating fluidized bed process for shortening the contact time of hydrocarbon and catalyst has been proposed.
- the hydrocarbon generates by-products such as carbon dioxide and carbon monoxide, which are not olefins, rapidly reacting with the catalyst at the initial stage of the reaction. There is this.
- Pretreatment of the catalyst by supplying a reducing gas to a catalyst for preparing olefins from hydrocarbons (step 1);
- step 2 Preparing an olefin from a hydrocarbon using the catalyst pretreated in step 1 (step 2);
- step 3 Separating the catalyst used in step 2 from the prepared olefin and regenerating the separated catalyst (step 3); And
- step 4 Recycling the catalyst regenerated in step 3 to the process of step 1 (step 4);
- the above steps 1 to 4 are repeatedly performed to provide a continuous reaction-regeneration and fluidized olefin production method for continuously regenerating the catalyst and preparing the olefin.
- a hydrocarbon supply unit supplying a hydrocarbon to the hydrocarbon reaction unit
- a reducing gas supply unit for supplying a reducing gas capable of causing an exothermic reaction with oxygen species contained in the catalyst
- a catalyst supply unit supplying the catalyst pretreated in the catalyst pretreatment unit to the hydrocarbon reaction unit;
- It provides a continuous reaction-regeneration and fluidized olefin production apparatus for performing the production method comprising a; air reaction unit for regenerating the catalyst separated in the separation unit.
- a hydrocarbon supply unit supplying a hydrocarbon to the hydrocarbon reaction unit
- a reducing gas supply unit for supplying a reducing gas capable of causing an exothermic reaction with oxygen species contained in the catalyst
- a catalyst supply unit supplying the catalyst pretreated in the catalyst pretreatment unit to the hydrocarbon reaction unit;
- step 1 Supplying a reducing gas to the catalyst pretreatment unit to pretreat the catalyst for preparing the olefin from the hydrocarbon (step 1);
- step 2 Supplying the catalyst pretreated in step 1 to the hydrocarbon reaction part through a catalyst supply part, and supplying a hydrocarbon raw material to a hydrocarbon reaction part through a hydrocarbon supply part to prepare an olefin from a hydrocarbon (step 2);
- step 3 Separating the catalyst used in step 2 and the prepared olefin in the separation unit, and then introducing the separated catalyst into the air reaction unit to regenerate the catalyst (step 3); And
- step 4 introducing the catalyst regenerated in step 3 into the catalyst pretreatment unit (step 4).
- the reducing gas is a by-product produced during the preparation of the olefin from the hydrocarbon in step 2, it provides a method for recycling by-products generated during the production of olefin from a hydrocarbon.
- a process for supplying a reducing gas to the catalyst and pretreatment is added as compared to the conventional process, thereby improving the selectivity and yield of the olefin.
- the hydrocarbon is prevented from contacting the catalyst at the beginning of the reaction to be converted into unnecessary by-products, thereby facilitating the process of converting the hydrocarbon into olefins, and enabling efficient utilization of the catalyst.
- FIG. 2 is a schematic representation of an apparatus for implementing the method of the present invention
- Example 7 is a graph showing a comparison according to the presence or absence of reducing gas pretreatment of the catalyst in Example 6 and Comparative Example 2 of the present invention.
- Pretreatment of the catalyst by supplying a reducing gas to a catalyst for preparing olefins from hydrocarbons (step 1);
- step 2 Preparing an olefin from a hydrocarbon using the catalyst pretreated in step 1 (step 2);
- step 3 Separating the catalyst used in step 2 from the prepared olefin and regenerating the separated catalyst (step 3); And
- step 4 Recycling the catalyst regenerated in step 3 to the process of step 1 (step 4);
- the above steps 1 to 4 are repeatedly performed to provide a continuous reaction-regeneration and fluidized olefin production method for continuously regenerating the catalyst and preparing the olefin.
- step 1 is a step of pretreating the catalyst by supplying a reducing gas to a catalyst for preparing an olefin from a hydrocarbon.
- the production process of the invention relates in particular to a dehydrogenation process for producing olefins from hydrocarbons.
- the catalyst is generally used when preparing the olefin, and when preparing the olefin from the hydrocarbon through the catalyst in the prior art as shown in the graph of FIG. It can be seen that the temperature gradually decreases after that.
- an initial part of the reaction for example, about 5 seconds from the start of the reaction, corresponds to an unnecessary part for preparing the olefin.
- step 1 focuses on the generation of by-products when the temperature of the catalyst increases in the prior art, that is, in the graph of FIG. 1, and a section in which the temperature is increased by pretreatment of the catalyst before being supplied to the hydrocarbon. This is because the olefin can be produced immediately without a by-product section when the catalyst is fed with hydrocarbon.
- the pretreatment of step 1 may be performed by contacting the catalyst and the reducing gas for 0.5 to 5 seconds.
- the time range during which the contact is carried out specifies the extent to which the temperature of the catalyst is raised approximately, thereby pretreating the catalyst to an optimal state for olefin production. have.
- step 1 when the contact between the catalyst and the reducing gas is less than 0.5 seconds, the optimization of the catalyst according to the pretreatment of step 1 may not be achieved. When the contact between the catalyst and the reducing gas exceeds 5 seconds, the yield of the olefin is rather increased. Degradation problems may occur.
- the reducing gas of step 1 may include at least one hydrocarbon having a linear or branched C 1 to C 4 alkane structure.
- the reducing gas of step 1 may include at least one hydrocarbon having a linear or branched C 1 to C 4 alkene structure,
- the reducing gas of step 1 may include a gas such as carbon monoxide, hydrogen, ethylene, ethane, methane.
- the gas, such as carbon monoxide may react with oxygen on the surface of the highly reactive catalyst to pretreat the catalyst, and the temperature of the catalyst may increase due to the exotherm generated by the pretreatment.
- the catalyst of step 1 for example a metal oxide catalyst, may be a chemical reaction of hydrogen, which is a kind of reducing gas, and M x O y + H 2 ⁇ M x ' O y ' + H 2 O.
- the reaction is an exothermic reaction in which water is generated, thereby increasing the temperature of the catalyst.
- the reducing gas of step 1 may be a by-product generated when preparing the olefin from a hydrocarbon.
- carbon monoxide, hydrogen, ethylene, ethane, methane and the like are usually generated as by-products.
- the production method of the present invention can be used as a reducing gas for pretreatment of the catalyst such as carbon monoxide generated as a by-product, there is an effect that can reduce the cost of the manufacturing process.
- step 2 is a step of preparing an olefin from a hydrocarbon using the catalyst pretreated in step 1 above.
- the catalyst of step 2 is pretreated by a reducing gas before reacting with hydrocarbons, so that the olefin can be produced more efficiently compared to the catalyst in the prior art, that is, a catalyst that has been introduced into the olefin production process without pretreatment. have.
- the catalyst in the state of which the temperature is increased through the pretreatment of step 1 may be produced without a by-product section.
- the olefin can be produced from a hydrocarbon. This not only enables the mass production of olefins, but also increases the efficiency in terms of economics of the process.
- the contact time between the pretreated catalyst and the raw material hydrocarbon may be 0.5 to 10 seconds, preferably 2 to 3 seconds.
- the contact time of the hydrocarbon and the catalyst is less than 0.5 seconds, there is a problem that the conversion rate of the hydrocarbon is lowered, and if the contact time is more than 10 seconds, the amount of active lattice oxygen participating in the reaction among the lattice oxygen of the catalyst is drastically reduced. Problems may occur in which the selectivity of olefins is reduced.
- the catalyst in contact with the hydrocarbon in step 2, that is, the catalyst pretreated in step 1 may be a metal oxide catalyst, in this case, the reaction in which the olefin is prepared from the hydrocarbon may be represented by the following scheme 1.
- M is at least one metal selected from the group consisting of chromium, vanadium, manganese, iron, cobalt, molybdenum, copper, zinc, cerium and nickel,
- the catalyst used in the above steps 1 and 2 may be a metal oxide, as shown in the above scheme, for example, may be in a form supported on a carrier.
- the metal oxide catalyst is an oxygen species carrier, and when the oxygen species carrier is used as a catalyst, a reaction occurs in which lattice oxygen on the catalyst reacts with hydrogen released from the hydrocarbon to generate water and olefins. Accordingly, the olefin selectivity is high, and the oxidative exothermic reaction of the desorbed hydrogen, which compensates for the lack of reaction energy due to the dehydrogenation endothermic reaction, proceeds, and the manufacturing method thereof is also simple, so that there is an advantage in that economical and mass production is possible.
- the carrier may be, for example, alumina, but is not limited thereto.
- the catalyst may be selected by selecting an appropriate material that can be used as a carrier of the catalyst.
- step 3 is a step of separating the catalyst reacted in step 2 with the prepared olefin and regenerating the separated catalyst.
- the metal oxide may be regenerated through the catalyst reacted in Step 2, for example, the reaction represented by Scheme 2 below.
- M x ' O y ' of Scheme 2 means a catalyst on which the reaction as in Scheme 1 is carried out
- Scheme 2 is a reaction to the reaction with oxygen after the catalyst reacted with the hydrocarbon is separated from the olefin through the separation unit It is shown to be performed by.
- step 4 is a step of recycling the catalyst regenerated in step 3 to the process of step 1.
- step 3 of the present invention By feeding the catalyst regenerated in step 3 of the present invention back to the process of step 1, the catalyst is recycled, thereby making it possible to produce olefins more economically.
- step 3 since the reaction in which the catalyst is regenerated in step 3 is exothermic, it is possible to raise the temperature of the catalyst through the generated heat energy, and thus, pretreatment may be performed more smoothly through the reducing gas in step 1 being recycled.
- the production method of the present invention can not only improve the yield of olefin production through the pretreatment of the catalyst, but also can regenerate and repeatedly use the catalyst used in the production of olefin, thereby further improving the economics of the process.
- the olefin can be continuously produced.
- the production method of the present invention is a method that can produce olefins more economically than in the prior art, in which there was no pretreatment for the catalyst. Therefore, in the case of the olefin according to the present invention there is an advantage that is more economical than the prior art.
- a hydrocarbon supply unit supplying a hydrocarbon to the hydrocarbon reaction unit
- a reducing gas supply unit for supplying a reducing gas capable of causing an exothermic reaction with oxygen species contained in the catalyst
- a catalyst supply unit supplying the catalyst pretreated in the catalyst pretreatment unit to the hydrocarbon reaction unit;
- It provides a continuous reaction-regeneration and fluidized olefin production apparatus comprising a; air reaction unit for regenerating the catalyst separated in the separation unit.
- a reducing gas capable of causing an exothermic reaction with active oxygen species included in the catalyst is supplied to the catalyst pretreatment unit 60.
- the catalyst pretreated by the reducing gas in the catalyst pretreatment unit is supplied to the hydrocarbon reaction unit 30 through a catalyst supply unit 40, and the reaction in which the olefin is generated from the supplied hydrocarbon is performed in the hydrocarbon reaction unit. .
- the olefin produced in the hydrocarbon reaction unit may be obtained by being separated from the catalyst used in the separation unit 50, and the catalyst separated in the separation unit may be supplied to the air reaction unit 20 to be regenerated.
- the catalyst regenerated in the air reaction unit 20 may be supplied again to the catalyst pretreatment unit 60, and then supplied to the hydrocarbon reaction unit again after the pretreatment.
- the manufacturing apparatus is a device for performing the olefin production method of the present invention as described above, it is possible to produce the olefin from the hydrocarbon while performing the pretreatment process of the catalyst through a reducing gas, by the pre-treatment more than before Olefin can be produced in high yields.
- a hydrocarbon supply unit supplying a hydrocarbon to the hydrocarbon reaction unit
- a reducing gas supply unit for supplying a reducing gas capable of causing an exothermic reaction with oxygen species contained in the catalyst
- a catalyst supply unit supplying the catalyst pretreated in the catalyst pretreatment unit to the hydrocarbon reaction unit;
- step 1 Supplying a reducing gas to the catalyst pretreatment unit to pretreat the catalyst for preparing the olefin from the hydrocarbon (step 1);
- step 2 Supplying the catalyst pretreated in step 1 to the hydrocarbon reaction part through a catalyst supply part, and supplying a hydrocarbon raw material to a hydrocarbon reaction part through a hydrocarbon supply part to prepare an olefin from a hydrocarbon (step 2);
- step 3 Separating the catalyst used in step 2 and the prepared olefin in the separation unit, and then introducing the separated catalyst into the air reaction unit to regenerate the catalyst (step 3); And
- step 4 introducing the catalyst regenerated in step 3 into the catalyst pretreatment unit (step 4).
- the reducing gas is a by-product produced during the preparation of the olefin from the hydrocarbon in step 2, it provides a method for recycling by-products generated during the production of olefin from a hydrocarbon.
- the recycling method of the present invention includes the same technical features as described in the method for producing and manufacturing the olefins described above, but relates to a method for recycling the by-product as a reducing gas for pretreatment of the catalyst, Since it is as described above except used as a reducing gas, the description thereof is omitted.
- the recycling method of the present invention is to use by-products, ie, by-products of carbon monoxide, hydrogen, methane, ethane, ethylene and the like generated as a reducing gas for pretreatment of the catalyst when preparing olefins from hydrocarbons.
- Step 1 ⁇ -Al 2 O 3 having a size of 45-120 um obtained by spray drying and calcining an alumina sol was prepared as a carrier.
- Step 2 To impregnate the metal oxide on the carrier prepared in Step 1, a wet impregnation method was used. Specifically, the alumina carrier prepared in step 1 was immersed in dilute CrO 3 precursor solution, it was left at room temperature for 12 hours, and then the alumina carrier was dried in a 120 ° C. oven.
- the dried carrier was calcined at 700 ° C. for 6 hours, whereby 17.5 wt% Chromium oxide / Alumina (Al 2 O 3 ) Catalyst was prepared.
- Step 1 Pretreatment of hydrogen (H 2 ) with the catalyst through a reducing gas supply prior to supplying the chromium oxide / alumina (Al 2 O 3 ) catalyst prepared in the above preparation to the reaction via the catalyst supply To the temperature, and the temperature of the catalyst passing through the catalyst supply was raised to 660 °C.
- Step 2 The catalyst heated in step 1 was supplied to the hydrocarbon reaction section, and propane was supplied to the hydrocarbon reaction section through the hydrocarbon supply section to prepare propylene.
- Step 3 The catalyst reacted with propylene prepared in step 2 was separated in a separation unit to obtain propylene, and the reacted catalyst was fed back into the air reaction unit to regenerate.
- Step 4 The catalyst regenerated in the air reaction unit was repeatedly performed in step 1, and then supplied to the hydrocarbon reaction unit.
- Propylene was prepared in the same manner as in Example 1 except for supplying carbon monoxide (CO) instead of hydrogen as the reducing gas in Step 1 of Example 1 of the present invention.
- CO carbon monoxide
- Propylene was prepared in the same manner as in Example 1 except for supplying methane (CH 4 ) instead of hydrogen as a reducing gas in Step 1 of Example 1 of the present invention.
- Propylene was prepared in the same manner as in Example 1 except that ethylene (C 2 H 4 ) instead of hydrogen was supplied as the reducing gas in Step 1 of Example 1 of the present invention.
- Propylene was prepared in the same manner as in Example 1 except that ethane (C 2 H 6 ) instead of hydrogen was supplied as the reducing gas in Step 1 of Example 1 of the present invention.
- Propylene was prepared in the same manner as in Example 1 except that no reducing gas was used in Step 1 of Example 1 of the present invention.
- Chromium oxide / Alumina (Al 2 O 3 ) prepared in the preparation example of the present invention 0.4 g of the catalyst was fixed on a fritz in a reactor made of quartz, and the furnace temperature was maintained at 630 ° C., followed by propane. The space velocity was 8,230 liter C3 / (kg cat -hr), through which propylene was produced.
- Example 1 Example 2
- Example 3 Example 3 Reducing gas H 2 CO CH 4 CH 4 Reduction Gas Supply (mol / Cr mol) 0.0443 0.0394 0.0361 0.0354 Catalyst Supply Part Catalyst Temperature ( o C) 597 660 660 661 660 Catalyst / propane ratio (weight / weight) 31.5 26.2 21 27.6 24.1 Propane Conversion Rate (%) 42.2 49.0 42.32 45.33 39.09 Propylene Yield (%) 30.76 34.15 30.95 34.69 31.04
- Example 3 Example 4 Example 5 Reducing gas CH 4 C 2 H 4 C 2 H 6 Reduction Gas Supply (mol / Cr mol) 0.0529 0.0537 0.0762 Catalyst Supply Part Catalyst Temperature ( o C) 670 670 670 Catalyst / propane ratio (weight / weight) 38.6 38 37.5 Propane Conversion Rate (%) 47.53 51.01 50.01 Propylene Yield (%) 35.19 40.08 44.51
- the propylene yield increased from 30.76% to 44.51% as the catalyst was pretreated with reducing gas.
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- Catalysts (AREA)
Abstract
La présente invention concerne un procédé permettant successivement de faire réagir-régénérer et préparer une oléfine de type fluide après un pré-traitement avec un gaz réducteur, et plus spécifiquement, un procédé permettant successivement de faire réagir-régénérer et préparer une oléfine de type fluide, le procédé comprenant les étapes consistant à : pré-traiter un catalyseur en lui administrant un gaz réducteur, le catalyseur servant à préparer l'oléfine à partir de l'hydrocarbure (étape 1); préparer une oléfine à partir de l'hydrocarbure à l'aide du catalyseur pré-traité de l'étape 1 (étape 2); séparer le catalyseur utilisé dans l'étape 2 et l'oléfine préparée, puis régénérer le catalyseur séparé (étape 3); et faire recirculer le catalyseur régénéré dans l'étape 3 pour le processus de l'étape 1 (étape 4), les étapes 1 à 4 étant réalisées de manière répétée de façon à régénérer le catalyseur et à préparer l'oléfine successivement. Comparé aux procédés classiques, le procédé de préparation de la présente invention comporte, en plus, une phase de pré-traitement d'un catalyseur en administrant à celui-ci un gaz réducteur, ce qui permet d'améliorer la sélectivité et le rendement de l'oléfine. En outre, l'invention permet d'éviter la conversion de l'hydrocarbure en sous-produit inutile par contact du catalyseur à un stade réactionnel trop précoce, ce qui facilite la conversion de l'hydrocarbure en oléfine et permet d'utiliser efficacement le catalyseur.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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KR20150092953 | 2015-06-30 | ||
KR10-2015-0092953 | 2015-06-30 |
Publications (1)
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WO2017003014A1 true WO2017003014A1 (fr) | 2017-01-05 |
Family
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Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
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PCT/KR2015/008671 WO2017003014A1 (fr) | 2015-06-30 | 2015-08-19 | Procédé pour successivement faire réagir-régénérer et préparer une oléfine de type fluide après prétraitement avec un gaz réducteur |
PCT/KR2016/000612 WO2017003059A1 (fr) | 2015-06-30 | 2016-01-20 | Procédé à étapes successives de réaction-régéneration et de préparation d'oléfine |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/KR2016/000612 WO2017003059A1 (fr) | 2015-06-30 | 2016-01-20 | Procédé à étapes successives de réaction-régéneration et de préparation d'oléfine |
Country Status (2)
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KR (1) | KR101807221B1 (fr) |
WO (2) | WO2017003014A1 (fr) |
Families Citing this family (4)
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KR102179574B1 (ko) | 2017-06-07 | 2020-11-16 | 에스케이가스 주식회사 | 환원 전처리를 포함하는 올레핀 제조 방법 |
KR102179176B1 (ko) | 2017-06-07 | 2020-11-16 | 에스케이가스 주식회사 | 순환유동층 공정을 이용한 올레핀의 제조방법 |
KR20200083760A (ko) | 2018-12-28 | 2020-07-09 | 에스케이가스 주식회사 | 순환유동층 공정을 이용한 올레핀의 제조방법 |
CN111804199B (zh) * | 2020-07-31 | 2022-06-03 | 广东博智林机器人有限公司 | 搅拌结构及具有其的搅拌器 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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JPS58177922A (ja) * | 1982-04-12 | 1983-10-18 | Mitsubishi Gas Chem Co Inc | オレフインの製造方法 |
JPH01110635A (ja) * | 1987-08-08 | 1989-04-27 | China Petro Chem Corp Res Inst Of Petroleum Processing | 炭化水素の接触転化によるガス状オレフインの製造方法 |
JPH08198782A (ja) * | 1994-10-18 | 1996-08-06 | Basf Ag | オレフィン系不飽和化合物を製造するための再生方法 |
JPH0975734A (ja) * | 1995-09-11 | 1997-03-25 | Mitsubishi Gas Chem Co Inc | 触媒の再生方法 |
JP2010531221A (ja) * | 2007-06-25 | 2010-09-24 | サウディ ベーシック インダストリーズ コーポレイション | 二酸化炭素の合成ガスへの接触水素化 |
Family Cites Families (5)
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US5194417A (en) * | 1991-12-05 | 1993-03-16 | Quantum Chemical Corporation | Pretreatment of palladium-gold catalysts useful in vinyl acetate synthesis |
JP5331305B2 (ja) * | 2004-03-31 | 2013-10-30 | 公益財団法人名古屋産業科学研究所 | 水素化促進剤、水素化触媒及びアルケン化合物の製法 |
RU2349569C2 (ru) * | 2004-07-28 | 2009-03-20 | Мейденся Корпорейшн | Способ получения ароматического углеводорода и водорода |
KR100651418B1 (ko) | 2006-03-17 | 2006-11-30 | 에스케이 주식회사 | 고속유동층을 이용하여 탄화수소 원료로부터 경질 올레핀을제조하는 접촉분해 공정 |
EP2975013A1 (fr) * | 2013-04-03 | 2016-01-20 | Scg Chemicals Co. Ltd. | Catalyseur de conversion de paraffine en oléfine |
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2015
- 2015-08-19 WO PCT/KR2015/008671 patent/WO2017003014A1/fr active Application Filing
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2016
- 2016-01-19 KR KR1020160006605A patent/KR101807221B1/ko active IP Right Grant
- 2016-01-20 WO PCT/KR2016/000612 patent/WO2017003059A1/fr active Application Filing
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58177922A (ja) * | 1982-04-12 | 1983-10-18 | Mitsubishi Gas Chem Co Inc | オレフインの製造方法 |
JPH01110635A (ja) * | 1987-08-08 | 1989-04-27 | China Petro Chem Corp Res Inst Of Petroleum Processing | 炭化水素の接触転化によるガス状オレフインの製造方法 |
JPH08198782A (ja) * | 1994-10-18 | 1996-08-06 | Basf Ag | オレフィン系不飽和化合物を製造するための再生方法 |
JPH0975734A (ja) * | 1995-09-11 | 1997-03-25 | Mitsubishi Gas Chem Co Inc | 触媒の再生方法 |
JP2010531221A (ja) * | 2007-06-25 | 2010-09-24 | サウディ ベーシック インダストリーズ コーポレイション | 二酸化炭素の合成ガスへの接触水素化 |
Also Published As
Publication number | Publication date |
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WO2017003059A1 (fr) | 2017-01-05 |
KR20170003371A (ko) | 2017-01-09 |
KR101807221B1 (ko) | 2018-01-18 |
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