CN113816819A - Method and system for preparing ethylene by coupling methane oxidative coupling reaction and ethane catalytic dehydrogenation reaction - Google Patents
Method and system for preparing ethylene by coupling methane oxidative coupling reaction and ethane catalytic dehydrogenation reaction Download PDFInfo
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- CN113816819A CN113816819A CN202010559842.6A CN202010559842A CN113816819A CN 113816819 A CN113816819 A CN 113816819A CN 202010559842 A CN202010559842 A CN 202010559842A CN 113816819 A CN113816819 A CN 113816819A
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 218
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 238000005691 oxidative coupling reaction Methods 0.000 title claims abstract description 71
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 61
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 39
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000005977 Ethylene Substances 0.000 title claims abstract description 30
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 14
- 230000008878 coupling Effects 0.000 title claims abstract description 11
- 238000010168 coupling process Methods 0.000 title claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 131
- 238000006243 chemical reaction Methods 0.000 claims abstract description 109
- 239000000463 material Substances 0.000 claims abstract description 51
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000001301 oxygen Substances 0.000 claims abstract description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 67
- 239000000377 silicon dioxide Substances 0.000 claims description 39
- 229910052906 cristobalite Inorganic materials 0.000 claims description 34
- 229910052681 coesite Inorganic materials 0.000 claims description 32
- 229910052682 stishovite Inorganic materials 0.000 claims description 32
- 229910052905 tridymite Inorganic materials 0.000 claims description 32
- 239000011734 sodium Substances 0.000 claims description 26
- 239000011572 manganese Substances 0.000 claims description 19
- 229910003111 Mg(Al)O Inorganic materials 0.000 claims description 18
- 229910002846 Pt–Sn Inorganic materials 0.000 claims description 18
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 12
- 229910002113 barium titanate Inorganic materials 0.000 claims description 12
- 229910052708 sodium Inorganic materials 0.000 claims description 12
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 11
- 238000012546 transfer Methods 0.000 claims description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 9
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 8
- 229910052721 tungsten Inorganic materials 0.000 claims description 8
- 239000010937 tungsten Substances 0.000 claims description 8
- 150000002910 rare earth metals Chemical class 0.000 claims description 7
- 229910002761 BaCeO3 Inorganic materials 0.000 claims description 6
- 101100065715 Lytechinus variegatus ETS-2 gene Proteins 0.000 claims description 6
- 229910002835 Pt–Ir Inorganic materials 0.000 claims description 6
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 6
- 229910021523 barium zirconate Inorganic materials 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052878 cordierite Inorganic materials 0.000 claims description 2
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 description 8
- 239000001569 carbon dioxide Substances 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 229910001026 inconel Inorganic materials 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000005120 petroleum cracking Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- -1 polyethylene, ethylene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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
- C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
- C07C2/82—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling
- C07C2/84—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling catalytic
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3335—Catalytic processes with metals
- C07C5/3337—Catalytic processes with metals of the platinum group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/32—Manganese, technetium or rhenium
- C07C2523/34—Manganese
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/56—Platinum group metals
- C07C2523/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the field of methane oxidative coupling reaction, and discloses a method and a system for preparing ethylene by coupling methane oxidative coupling reaction and ethane catalytic dehydrogenation reaction, wherein the method is carried out in a fixed bed casing pipe reactor containing at least two layers of casing pipes, and at least one pipe of the casing pipes is filled with a catalyst A for the methane oxidative coupling reaction for carrying out the methane oxidative coupling reaction; and a tube adjacent thereto is packed with a catalyst B for catalytic dehydrogenation reaction of ethane for carrying out catalytic dehydrogenation reaction of ethane, the method comprising: introducing a reaction material I containing methane and oxygen into a pipe filled with the catalyst A to perform the oxidative coupling reaction of methane; introducing a reaction material II containing ethane into a reaction tube filled with the catalyst B to perform the ethane catalytic dehydrogenation reaction. The invention solves the problem that the heat is difficult to remove at high temperature in the current methane oxidation reaction, and reduces the risk of high-temperature runaway.
Description
Technical Field
The invention relates to the field of methane oxidative coupling reaction, in particular to a method and a system for preparing ethylene by coupling methane oxidative coupling reaction and ethane catalytic dehydrogenation reaction.
Background
Ethylene is an important substrate in the petrochemical industry and is mainly used for producing chemical products such as polyethylene, ethylene oxide, vinyl chloride, styrene and the like. Ethylene is the most important basic organic chemical raw material, and its production has long been dependent on petroleum cracking routes, and the problems of environmental pollution and the like caused by the ethylene are becoming serious. In recent years, the price of crude oil is continuously rising to cause the price of ethylene cracking raw materials to rise, and the phenomenon of short supply and short demand of the ethylene cracking raw materials is also very prominent.
The theoretically most efficient method for producing ethylene is oxidative coupling of methane, which is the most abundant component in natural gas and is cheaper than other feedstocks. Therefore, Oxidative Coupling of Methane (OCM) has become a major research focus in various countries,
in the research of OCM catalyst system, a supported catalyst using silicon dioxide as a carrier and sodium tungstate and manganese as active components is one of the systems with the best performance, but the common catalyst can react at high temperature, the reaction temperature is 750-850 ℃ or even higher, and the reaction heat is not easy to be removed at high temperature, thereby causing the problem of temperature runaway to easily occur.
Disclosure of Invention
The invention aims to overcome the defect that the high temperature is easy to fly in the methane oxidative coupling reaction in the prior art.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing ethylene by coupling an oxidative coupling reaction of methane and a catalytic dehydrogenation reaction of ethane, the method being performed in a fixed-bed loop reactor comprising at least two loops, at least one of the loops being filled with a catalyst a for the oxidative coupling reaction of methane for performing the oxidative coupling reaction of methane, the reaction temperature of the catalyst a being not lower than 700 ℃; and a tube adjacent thereto is packed with a catalyst B for catalytic dehydrogenation reaction of ethane for carrying out the catalytic dehydrogenation reaction of ethane, the catalyst B being selected from Pt/SiO2、Pt-In/SiO2、Pt/Mg(Al)O、Pt-Sn/Mg(Al)O、Pt-Ir/Mg(Al)O、Pt-Sn/Mg(Ga)(Al)O、Pt-Zn/ETS-2、Cr/BaZrO3、Cr/BaCeO3、Cr/MCM-41、Ga/HZSM-5、P-Mo/ZSM-5、Pd-In/SiO2At least one of;
the method comprises the following steps: introducing a reaction material I containing methane and oxygen into a pipe filled with the catalyst A to perform the oxidative coupling reaction of methane; introducing a reaction material II containing ethane into a reaction tube filled with the catalyst B to perform the catalytic dehydrogenation reaction of the ethane;
the fixed bed shell and tube reactor is made of a material which enables heat transfer between tubes for performing the methane oxidative coupling reaction and the ethane catalytic dehydrogenation reaction.
The second aspect of the invention provides a system for preparing ethylene by coupling methane oxidative coupling reaction and ethane catalytic dehydrogenation reaction, which comprises a fixed bed casing reactor comprising at least two layers of casings, wherein at least one pipe of each casing is filled with a catalyst A for the methane oxidative coupling reaction for carrying out the methane oxidative coupling reaction, and the reaction temperature of the catalyst A is not lower than 700 ℃; and a tube adjacent thereto is packed with a catalyst B for catalytic dehydrogenation reaction of ethane for carrying out the catalytic dehydrogenation reaction of ethane, the catalyst B being selected from Pt/SiO2、Pt-In/SiO2、Pt/Mg(Al)O、Pt-Sn/Mg(Al)O、Pt-Ir/Mg(Al)O、Pt-Sn/Mg(Ga)(Al)O、Pt-Zn/ETS-2、Cr/BaZrO3、Cr/BaCeO3、Cr/MCM-41、Ga/HZSM-5、P-Mo/ZSM-5、Pd-In/SiO2At least one of;
the fixed bed shell and tube reactor is made of a material which enables heat transfer between tubes for performing the methane oxidative coupling reaction and the ethane catalytic dehydrogenation reaction.
Compared with the prior art, the invention has at least the following advantages:
the method disclosed by the invention has the advantages that the oxidative coupling reaction of methane and the catalytic dehydrogenation reaction of ethane are coupled, and the defect of difficulty in heat removal in the high-temperature reaction of the existing methane oxidation reaction is overcome through heat transfer, so that the risk of temperature runaway at high temperature is reduced.
Meanwhile, the method provided by the invention couples the methane oxidative coupling reaction with the ethane catalytic dehydrogenation reaction, and supplies the heat released by the methane oxidative coupling reaction to the ethane catalytic dehydrogenation reaction, so that the problems of high heating temperature and high energy consumption required by the ethane catalytic dehydrogenation reaction are solved, the heat is fully utilized, the optimized utilization of the energy is realized, the industrial popularization is facilitated, and the method has a wide application prospect.
Additional features and advantages of the invention will be described in detail in the detailed description which follows.
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.
In the present invention, the reaction temperature refers to a temperature at which the catalyst can play a catalytic role to promote the reaction, and is generally within an interval range. Thus, the reaction temperature of the catalyst as defined herein is within a temperature range such as T1-T2, and means that the temperature at which the catalyst catalyzes to promote reaction is within the temperature range T1-T2, which may be any small range within the range T1-T2, or T1-T2.
As described above, the first aspect of the present invention provides a method for preparing ethylene by coupling an oxidative coupling reaction of methane and a catalytic dehydrogenation reaction of ethane, the method being performed in a fixed-bed tubular reactor comprising at least two tubular casings, at least one of the tubular casings being filled with a catalyst a for the oxidative coupling reaction of methane for performing the oxidative coupling reaction of methane, the reaction temperature of the catalyst a being not lower than 700 ℃; and a tube adjacent thereto is packed with a catalyst B for catalytic dehydrogenation reaction of ethane for carrying out the catalytic dehydrogenation reaction of ethane, the catalyst B being selected from Pt/SiO2、Pt-In/SiO2、Pt/Mg(Al)O、Pt-Sn/Mg(Al)O、Pt-Ir/Mg(Al)O、Pt-Sn/Mg(Ga)(Al)O、Pt-Zn/ETS-2、Cr/BaZrO3、Cr/BaCeO3、Cr/MCM-41、Ga/HZSM-5、P-Mo/ZSM-5、Pd-In/SiO2At least one of;
the method comprises the following steps: introducing a reaction material I containing methane and oxygen into a pipe filled with the catalyst A to perform the oxidative coupling reaction of methane; introducing a reaction material II containing ethane into a reaction tube filled with the catalyst B to perform the catalytic dehydrogenation reaction of the ethane;
the fixed bed shell and tube reactor is made of a material which enables heat transfer between tubes for performing the methane oxidative coupling reaction and the ethane catalytic dehydrogenation reaction.
In the present invention, the adjacent pipe means a pipe adjacent to a pipe for performing the oxidative coupling reaction of methane, and may be a single pipe or a plurality of pipes, for example, when the oxidative coupling reaction of methane is performed in a single pipe, the ethane catalytic dehydrogenation reaction may be performed in one or two adjacent pipes, and the present invention is not limited to the above-mentioned cases, and a person skilled in the art should not understand that the present invention is limited thereto.
Preferably, the fixed-bed double-layer casing tube reactor is a fixed-bed double-layer casing tube reactor, the methane oxidative coupling reaction is performed in an outer tube of the fixed-bed double-layer casing tube reactor, and the ethane catalytic dehydrogenation reaction is performed in an inner tube of the fixed-bed double-layer casing tube reactor.
In the present invention, the reaction material II may further contain at least one gas selected from hydrogen, nitrogen and inert gas in addition to ethane, for example, the reaction material II is a mixed gas of ethane and nitrogen, wherein the molar ratio of ethane to nitrogen is 1: 1 to 50; and if the reaction material II is a mixed gas of ethane and hydrogen, wherein the molar ratio of the ethane to the hydrogen is 1: 0.2-5.
Preferably, the reaction temperature of the catalyst A is 750-900 ℃.
Preferably, the reaction temperature of the catalyst B is 500-750 ℃, more preferably 550-650 ℃.
In the invention, the content of the active component in the catalyst B is 0.1-10 wt% in terms of element, based on the total weight of the catalyst B.
Preferably, according to the invention, In order to obtain a higher olefin selectivity, the catalyst B is chosen from Pt-In/SiO2And at least one of Pt-Sn/Mg (Al) O.
According to another preferred embodiment of the present invention, the catalyst a comprises a carrier and an active component loaded on the carrier, wherein the active component comprises a manganese element, a tungsten element, an alkali metal element, and optionally further comprises a rare earth metal element.
Preferably, based on the total weight of the catalyst a, the content of the manganese element is 1 to 10 wt%, the content of the tungsten element is 2 to 20 wt%, the content of the alkali metal element is 0.5 to 5 wt%, and the content of the rare earth metal element is 0 to 1 wt%.
Further preferably, in the catalyst a, the active component includes manganese element, tungsten element, sodium element, and optionally further includes rare earth metal element; the carrier is selected from at least one of silica, alumina, barium titanate, molecular sieve, cristobalite, and cordierite.
More preferably, in order to obtain higher olefin selectivity, the catalyst a is selected from at least one of sodium tungstate-manganese/silica, sodium tungstate-manganese-rare earth metal/silica, sodium tungstate-manganese/barium titanate, sodium tungstate-manganese-rare earth metal/barium titanate.
Even more preferably, the catalyst A is selected from modified or unmodified Na2WO4-Mn/SiO2And modified or unmodified Na2WO4-Mn/BaTiO3At least one of (1).
Modified Na as described in the invention2WO4-Mn/SiO2And the modified Na2WO4-Mn/BaTiO3The method comprises the steps of regulating and controlling by physical means such as microwave, ultrasonic and the like in the preparation process so as to improve the catalytic performance of the catalyst; the method also comprises the step of carrying out doping modification on the catalyst by adopting doping elements, wherein the doping elements are respectively and independently selected from at least one of alkaline earth metal elements, alkali metal elements and rare earth metal elements, and the content of the doping elements is 0.01-5 wt% calculated by the total weight of the modified catalyst.
In the present invention, the catalyst a and the catalyst B may be obtained commercially or may be obtained by self-production according to a method disclosed in a known literature.
Preferably, the loading weight ratio of the catalyst a to the catalyst B is 1: 0.1 to 10, more preferably 1: 0.2 to 5, more preferably 1: 0.3 to 3, thus, the catalyst A and the catalyst B are matched, so that the conversion rate of methane and ethane is higher, and the reaction energy consumption is lower.
Preferably, the space velocity of the methane oxidative coupling reaction is 0.1-10 ten thousand mL-g based on the methane contained in the reaction material I-1·h-1More preferably 0.2 to 8 ten thousand mL g-1·h-1。
Preferably, in the methane oxidative coupling reaction, the molar ratio of the used methane to the used oxygen is 1-10: 1, more preferably 3 to 10: 1.
preferably, the space velocity of the ethane catalytic dehydrogenation reaction is 0.1-6 ten thousand mL-g based on the ethane contained in the reaction material II-1·h-1More preferablyIs 0.5-5 ten thousand mL.g-1·h-1。
In the present invention, the reaction material I and the reaction material II may be in a cocurrent operation or a countercurrent operation.
Particularly preferably, in the fixed-bed double-pipe reactor, the reaction material I and the reaction material II run in a countercurrent mode, and the countercurrent mode means that the running directions of the reaction material I and the reaction material II are opposite.
According to the invention, the reaction mass and the reaction products of the oxidative coupling of methane and the catalytic dehydrogenation of ethane are carried out in two reaction channels of the fixed-bed shell-and-tube reactor respectively during the whole reaction process, and the reaction products are respectively measured by a gas chromatograph.
In the present invention, the reaction material I and the reaction material II may be introduced into the fixed-bed shell-and-tube reactor at the same time or at certain time intervals, but preferably, the reaction material II is introduced at the time of introduction of the reaction material I for 1 to 5min, whereby heat can be more effectively utilized and costs can be saved.
The method disclosed by the invention has the advantages that the oxidative coupling reaction of methane and the catalytic dehydrogenation reaction of ethane are coupled, and the defect of difficulty in heat removal in the high-temperature reaction of the existing methane oxidation reaction is overcome through heat transfer, so that the risk of temperature runaway at high temperature is reduced.
Meanwhile, the invention couples the methane oxidative coupling reaction with the ethane catalytic dehydrogenation reaction, supplies the heat released by the methane oxidative coupling reaction to the ethane catalytic dehydrogenation reaction, solves the problems of high heating temperature and high energy consumption required by the ethane catalytic dehydrogenation reaction, fully utilizes the heat, realizes the optimized utilization of the energy, is beneficial to industrial popularization, and has wide application prospect.
As previously mentioned, a second aspect of the present invention provides a system for the production of ethylene by oxidative coupling of methane and catalytic dehydrogenation of ethane, comprising a fixed-bed tubular reactor comprising at least two tubular sleeves, at least one of said sleeves being filled with a gas for the oxidation of methaneThe catalyst A for coupling reaction is used for carrying out the methane oxidative coupling reaction, and the reaction temperature of the catalyst A is not lower than 700 ℃; and a tube adjacent thereto is packed with a catalyst B for catalytic dehydrogenation reaction of ethane for carrying out the catalytic dehydrogenation reaction of ethane, the catalyst B being selected from Pt/SiO2、Pt-In/SiO2、Pt/Mg(Al)O、Pt-Sn/Mg(Al)O、Pt-Ir/Mg(Al)O、Pt-Sn/Mg(Ga)(Al)O、Pt-Zn/ETS-2、Cr/BaZrO3、Cr/BaCeO3、Cr/MCM-41、Ga/HZSM-5、P-Mo/ZSM-5、Pd-In/SiO2At least one of;
the fixed bed shell and tube reactor is made of a material which enables heat transfer between tubes for performing the methane oxidative coupling reaction and the ethane catalytic dehydrogenation reaction.
In the second aspect of the present invention, the kind and the amount of the catalyst a and the catalyst B are the same as those of the catalyst a and the catalyst B described in the first aspect, and the description of the present invention is omitted, and a person skilled in the art should not be construed as a limitation to the present invention.
The specific type of material of the fixed-bed shell-and-tube reactor is not particularly required in the present invention, as long as heat transfer can be performed to achieve heat exchange between the methane oxidative coupling reaction and the ethane catalytic dehydrogenation reaction, and the material may be, for example, quartz, metal stainless steel, metal inconel, and the like, and preferably, metal stainless steel or metal inconel.
The present invention will be described in detail below by way of examples.
In the following examples, all the raw materials used are commercially available ones unless otherwise specified.
Catalyst A: na (Na)2WO4-Mn/SiO2The preparation method of the catalyst refers to CN111203283A, and the type and the amount of the raw materials are adjusted according to the requirement to obtain Na2WO4-Mn/SiO2In the catalyst, based on the total weight of the catalyst, the content of manganese element is 2 wt%, the content of tungsten element is 4.2 wt%, and the content of sodium element is 1.05 wt%;
Na2WO4-Mn/BaTiO3the preparation method of the catalyst refers to CN111203210A, and the type and the amount of the raw materials are adjusted according to the requirement to obtain Na2WO4-Mn/BaTiO3In the catalyst, based on the total weight of the catalyst, the content of manganese element is 2 weight percent, the content of tungsten element is 4 weight percent, and the content of sodium element is 1.02 weight percent;
catalyst B: Pt-In/SiO2Catalyst references (WEGENER E C, WU Z, TSENG H-T, et al, Structure and reactivity of Pt-In interactive nanoparticles: high selectivity catalysts for ethane dehydrogenation [ J)]Catalysis Today,2018(299):146-2In the catalyst, based on the total weight of the catalyst, the content of the Pt element is 0.3 weight percent, and the content of the In element is 0.1 weight percent;
Pt-Sn/Mg (Al) O catalyst references (GALVITA V, SIDDIQI G, SUN Pingging, et al. ethane dehydrogenation on Pt/Mg (Al) O and Pt-Sn/Mg (Al) O catalysts [ J ]. Journal of Catalysis,2010(271):209-219.) were prepared, wherein in the Pt-Sn/Mg (Al) O catalyst, the content of the Pt element was 0.2 wt% and the content of the Sn element was 0.05 wt% based on the total weight of the catalyst.
In the following examples, the reaction products of the oxidative coupling of methane reaction and the catalytic dehydrogenation of ethane were determined by means of an Agilent gas chromatograph, model 7890A, manufactured by Agilent.
In the following examples, the fixed-bed double-layered reactors were all made of Inconel metal.
In the following examples, the parameters involved are calculated by the following formula:
reaction material I:
methane conversion ═ molar amount of methane consumed by the reaction/total initial molar amount of methane × 100%
Ethylene selectivity-the molar amount of methane consumed to form ethylene/the molar amount of methane consumed for the reaction x 100%
Ethane selectivity-the molar amount of methane consumed for ethane formation/the molar amount of methane consumed for reaction x 100%
Selectivity to carbo-carb-ol ethane + ethylene selectivity
Reaction mass II:
ethane conversion rate ═ molar amount of ethane consumed by reaction/initial molar amount of ethane × 100%
Ethylene selectivity ═ moles of ethane consumed to form ethylene/moles of ethane consumed in the reaction x 100%
In the following examples, both reaction mass I and reaction mass II were run in countercurrent, unless otherwise specified.
Example 1
0.6g of Na2WO4-Mn/SiO2The catalyst (catalyst A) was packed In the outer tube of a fixed bed double-shell tube reactor, and 0.2g of Pt-In/SiO2The catalyst (catalyst B) is filled in the inner tube of the fixed bed double-layer jacketed tube reactor;
heating the reactor to 750 ℃, and introducing methane and oxygen (reaction material I) into an outer pipe of the fixed bed double-layer sleeve reactor, wherein the flow rate of the methane is 30ml/min, and the flow rate of the oxygen is 10 ml/min; after the reaction material I is fed for 5min, setting the ethane flow rate to be 30ml/min, opening an ethane gas path valve, feeding ethane gas (reaction material II) into an inner tube of a fixed bed double-layer casing tube reactor, and carrying out an ethane catalytic dehydrogenation reaction in the inner tube of the reactor along with the increase of the bed temperature of the catalyst B in the reactor to 600 ℃;
the methane conversion rate and the selectivity of carbon dioxide in the outer pipe of the reactor, the ethane conversion rate and the selectivity of ethylene in the inner pipe of the reactor, and the hot spot temperature of the bed layer of the methane oxidative coupling reaction were measured by Agilent 7890A gas chromatography, and the specific results are shown in Table 1.
Example 2
In a similar manner to example 1, except that in this example:
the type and loading of the catalyst A, the type of the catalyst B, the space velocities of the reaction material I and the reaction material II, the gas type of the reaction material II and the heating temperature of the reactor are different from those of the example 1, and the rest is the same as that of the example 1;
specifically, the method comprises the following steps:
catalyst A: 0.2g of Na2WO4-Mn/BaTiO3A catalyst;
catalyst B: 0.2g of Pt-Sn/Mg (Al) O catalyst;
reaction material I: the flow rate of methane is 40ml/min, and the flow rate of oxygen is 10 ml/min;
reaction mass II: ethane + hydrogen, the flow rate of ethane is 40ml/min, and the flow rate of hydrogen is 60 ml/min;
the reactor was heated to 800 ℃ to perform the methane oxidative coupling reaction and the ethane catalytic dehydrogenation reaction, and the methane conversion and the selectivity to carbon dioxide in the outer tube of the reactor, the ethane conversion and the selectivity to ethylene in the inner tube of the reactor, and the hot spot temperature of the bed layer of the methane oxidative coupling reaction were measured, respectively, and the specific test results are shown in table 1.
Example 3
In a similar manner to example 1, except that in this example:
the type and loading of the catalyst A, the loading of the catalyst B, the space velocities of the reaction material I and the reaction material II, and the type of the reaction material II are different from those in example 1, and the rest are the same as those in example 1;
specifically, the method comprises the following steps:
catalyst A: 0.2g of Na2WO4-Mn/BaTiO3A catalyst;
catalyst B: 0.5g of Pt-In/SiO2A catalyst;
reaction material I: the flow rate of methane is 100ml/min, and the flow rate of oxygen is 20 ml/min;
reaction mass II: ethane + hydrogen, the flow rate of ethane is 300ml/min, and the flow rate of hydrogen is 100 ml/min;
the methane conversion rate and the selectivity of the carbon dioxide in the outer pipe of the reactor, the ethane conversion rate and the selectivity of the ethylene in the inner pipe of the reactor, and the hot spot temperature of the bed layer of the methane oxidative coupling reaction are respectively measured, and the specific test results are shown in table 1.
Example 4
In a similar manner to example 1, except that in this example:
the loading of catalyst A and catalyst B, the space velocities of the reaction material I and reaction material II, and the kind of the reaction material II are different from those of example 1, and the rest are the same as those of example 1;
specifically, the method comprises the following steps:
catalyst A: 0.2g of Na2WO4-Mn/SiO2A catalyst;
catalyst B: 0.1g of Pt-In/SiO2A catalyst;
reaction material I: the flow rate of methane is 60ml/min, and the flow rate of oxygen is 30 ml/min;
reaction mass II: ethane + nitrogen, ethane flow rate 70ml/min, nitrogen flow rate 70 ml/min;
the methane conversion rate and the selectivity of the carbon dioxide in the outer pipe of the reactor, the ethane conversion rate and the selectivity of the ethylene in the inner pipe of the reactor, and the hot spot temperature of the bed layer of the methane oxidative coupling reaction are respectively measured, and the specific test results are shown in table 1.
Example 5
In a similar manner to example 1, except that in this example:
the loading of catalyst A and catalyst B, the space velocities of the reaction mass I and reaction mass II, and the reaction heating temperature were different from those of example 1, and the rest were the same as those of example 1;
specifically, the method comprises the following steps:
catalyst A: 0.2g of Na2WO4-Mn/SiO2A catalyst;
catalyst B: 0.6g of Pt-In/SiO2A catalyst;
reaction material I: the flow rate of methane is 60ml/min, and the flow rate of oxygen is 30 ml/min;
reaction mass II: ethane, the ethane flow rate being 80 ml/min;
the reactor was heated to 850 ℃ to perform the methane oxidative coupling reaction and the ethane catalytic dehydrogenation reaction, and the methane conversion rate and the selectivity to carbon dioxide in the outer tube of the reactor, the ethane conversion rate and the selectivity to ethylene in the inner tube of the reactor, and the hot spot temperature of the bed layer of the methane oxidative coupling reaction were measured, respectively, and the specific test results are shown in table 1.
Example 6
In a similar manner to example 1, except that in this example:
the loading of catalyst a and catalyst B was different from that in example 1, but the kind of catalyst a and catalyst B in this example were the same as in example 1, respectively.
Specifically, the loading of catalyst A was 0.15g and the loading of catalyst B was 0.65 g.
The methane conversion rate and the selectivity of the carbon dioxide in the outer pipe of the reactor, the ethane conversion rate and the selectivity of the ethylene in the inner pipe of the reactor, and the hot spot temperature of the bed layer of the methane oxidative coupling reaction were measured, respectively, and the test results are shown in table 1.
Comparative example 1
In a similar manner to example 1, except that: the kind of catalyst B was different from that in example 1, but the loading of catalyst B was the same as that in example 1;
specifically, catalyst B was a Pt-Sn/alumina catalyst prepared with reference to CN106588544A, and the content of platinum was 0.2 wt% and the content of tin was 0.1 wt% based on the total weight of the catalyst.
The methane conversion rate and the selectivity of the carbon dioxide in the outer pipe of the reactor, the ethane conversion rate and the selectivity of the ethylene in the inner pipe of the reactor, and the hot spot temperature of the bed layer of the methane oxidative coupling reaction were measured, respectively, and the test results are shown in table 1.
Comparative example 2
The reaction procedure was similar to example 1, except that the coupling of the ethane catalytic dehydrogenation reaction was not performed in this comparative example.
Specifically, 0.6g of Na was added2WO4-Mn/SiO2The catalyst (catalyst A) is filled in the outer pipe of the fixed bed double-layer sleeve pipe reactor; heating the reactor to 750 ℃, introducing methane and oxygen into an outer pipe of a fixed bed double-layer casing pipe reactor, carrying out methane oxidation coupling reaction at a methane flow rate of 30ml/min and an oxygen flow rate of 10ml/min, measuring the methane conversion rate and the selectivity of the carbon dioxide in the outer pipe of the reactor and the bed hot spot temperature of the methane oxidation coupling reaction by an Agilent 7890A gas chromatography, and obtaining the specific resultSee table 1.
The hot-spot temperature of the bed for this comparative example was 970 deg.c, whereas the hot-spot temperature of the bed for the oxidative coupling of methane reaction in example 1 was 830 deg.c.
Therefore, the method provided by the invention can effectively reduce the temperature of the reaction bed layer by coupling the methane oxidative coupling and the ethane dehydrogenation reaction, and prevent temperature runaway during high-temperature reaction.
TABLE 1
Note: in table 1, the hot spot temperature of the bed refers to the hot spot temperature of the catalyst bed for performing the methane oxidative coupling reaction;
ethylene selectivity refers to the ethylene selectivity of reaction feed II.
The method has the advantages that the oxidative coupling reaction of methane and the catalytic dehydrogenation reaction of ethane are coupled, and the heat transfer is utilized, so that the defect that the heat is difficult to remove at high temperature in the current oxidative coupling reaction of methane is overcome, and the risk of temperature runaway at high temperature is reduced.
Meanwhile, the method provided by the invention couples the oxidative coupling reaction of methane with the catalytic dehydrogenation reaction of ethane, and supplies the heat released by the oxidative coupling reaction of methane to the catalytic dehydrogenation reaction of ethane, so that the problems of high temperature and high energy consumption required by the catalytic dehydrogenation reaction of ethane are solved.
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 (11)
1. Methane oxidative coupling reaction and ethane catalysisThe method for preparing the ethylene by coupling the chemical dehydrogenation reaction is characterized in that the method is carried out in a fixed bed sleeve reactor containing at least two layers of sleeves, at least one of the sleeves is filled with a catalyst A for the oxidative coupling reaction of the methane, and the catalyst A is used for carrying out the oxidative coupling reaction of the methane, and the reaction temperature of the catalyst A is not lower than 700 ℃; and a tube adjacent thereto is packed with a catalyst B for catalytic dehydrogenation reaction of ethane for carrying out the catalytic dehydrogenation reaction of ethane, the catalyst B being selected from Pt/SiO2、Pt-In/SiO2、Pt/Mg(Al)O、Pt-Sn/Mg(Al)O、Pt-Ir/Mg(Al)O、Pt-Sn/Mg(Ga)(Al)O、Pt-Zn/ETS-2、Cr/BaZrO3、Cr/BaCeO3、Cr/MCM-41、Ga/HZSM-5、P-Mo/ZSM-5、Pd-In/SiO2At least one of;
the method comprises the following steps: introducing a reaction material I containing methane and oxygen into a pipe filled with the catalyst A to perform the oxidative coupling reaction of methane; introducing a reaction material II containing ethane into a reaction tube filled with the catalyst B to perform the catalytic dehydrogenation reaction of the ethane;
the fixed bed shell and tube reactor is made of a material which enables heat transfer between tubes for performing the methane oxidative coupling reaction and the ethane catalytic dehydrogenation reaction.
2. The method as claimed in claim 1, wherein the reaction temperature of the catalyst A is 750-900 ℃;
preferably, the reaction temperature of the catalyst B is 500-750 ℃, more preferably 550-650 ℃.
3. The method according to claim 1 or 2, wherein the catalyst a comprises a carrier and an active component loaded on the carrier, the active component comprises a manganese element, a tungsten element, an alkali metal element, and optionally further comprises a rare earth metal element;
preferably, based on the total weight of the catalyst A, the content of the manganese element is 1-10 wt%, the content of the tungsten element is 2-20 wt%, the content of the alkali metal element is 0.5-5 wt%, and the content of the rare earth metal element is 0-1 wt%;
preferably, in the catalyst a, the active component includes manganese element, tungsten element, sodium element, and optionally further includes rare earth metal element; the carrier is selected from at least one of silica, alumina, barium titanate, molecular sieve, cristobalite, and cordierite.
4. The process of claim 3, wherein the catalyst A is selected from at least one of sodium tungstate-manganese/silica, sodium tungstate-manganese-rare earth metal/silica, sodium tungstate-manganese/barium titanate, sodium tungstate-manganese-rare earth metal/barium titanate.
5. The process of any of claims 1-4, wherein the loading weight ratio of catalyst A to catalyst B is 1: 0.1 to 10, preferably 1: 0.2 to 5, more preferably 1: 0.3-3.
6. The process according to any one of claims 1 to 5, wherein the space velocity of the oxidative coupling reaction of methane is from 0.1 to 10 ten thousand mL-g, based on the methane contained in the reaction material I-1·h-1Preferably 0.2 to 8 ten thousand mL g-1·h-1。
7. The process according to any one of claims 1 to 6, wherein in the oxidative coupling of methane, methane and oxygen are used in a molar ratio of 1 to 10: 1, preferably 3 to 10: 1.
8. the process of any one of claims 1 to 7, wherein the space velocity of the catalytic dehydrogenation reaction of ethane is from 0.1 to 6-ten thousand mL-g, based on the ethane contained in the reaction mass II-1·h-1Preferably 0.5 to 5 ten thousand mL g-1·h-1。
9. The process according to any one of claims 1 to 8, wherein in the fixed-bed shell-and-tube reactor, reaction material I and reaction material II are run in countercurrent.
10. The process according to any one of claims 1 to 9, wherein the fixed-bed double-shell tube reactor is a fixed-bed double-shell tube reactor, the oxidative coupling reaction of methane is carried out in an outer tube of the fixed-bed double-shell tube reactor, and the catalytic dehydrogenation reaction of ethane is carried out in an inner tube of the fixed-bed double-shell tube reactor.
11. A system for preparing ethylene by coupling methane oxidative coupling reaction and ethane catalytic dehydrogenation reaction is characterized by comprising a fixed bed casing reactor with at least two layers of casings, wherein at least one of the casings is filled with a catalyst A for the methane oxidative coupling reaction for carrying out the methane oxidative coupling reaction, and the reaction temperature of the catalyst A is not lower than 700 ℃; and a tube adjacent thereto is packed with a catalyst B for catalytic dehydrogenation reaction of ethane for carrying out the catalytic dehydrogenation reaction of ethane, the catalyst B being selected from Pt/SiO2、Pt-In/SiO2、Pt/Mg(Al)O、Pt-Sn/Mg(Al)O、Pt-Ir/Mg(Al)O、Pt-Sn/Mg(Ga)(Al)O、Pt-Zn/ETS-2、Cr/BaZrO3、Cr/BaCeO3、Cr/MCM-41、Ga/HZSM-5、P-Mo/ZSM-5、Pd-In/SiO2At least one of;
the fixed bed shell and tube reactor is made of a material which enables heat transfer between tubes for performing the methane oxidative coupling reaction and the ethane catalytic dehydrogenation reaction.
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