CN116020535A - Preparation method and application of efficient Fe/ZSM-5 catalyst - Google Patents
Preparation method and application of efficient Fe/ZSM-5 catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 103
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 69
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 63
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000002808 molecular sieve Substances 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 239000002253 acid Substances 0.000 claims abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 100
- 238000000034 method Methods 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 238000001354 calcination Methods 0.000 claims description 17
- 238000011068 loading method Methods 0.000 claims description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 238000005342 ion exchange Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 238000005832 oxidative carbonylation reaction Methods 0.000 claims description 5
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910001868 water Inorganic materials 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims 2
- 238000002390 rotary evaporation Methods 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- 238000011156 evaluation Methods 0.000 description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 13
- 241000894007 species Species 0.000 description 10
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000012263 liquid product Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 235000019253 formic acid Nutrition 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000005011 time of flight secondary ion mass spectroscopy Methods 0.000 description 4
- 238000002042 time-of-flight secondary ion mass spectrometry Methods 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- 239000012498 ultrapure water Substances 0.000 description 3
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 241000282326 Felis catus Species 0.000 description 2
- 102000020897 Formins Human genes 0.000 description 2
- 108091022623 Formins Proteins 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000006315 carbonylation Effects 0.000 description 2
- 238000005810 carbonylation reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
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- 238000005259 measurement Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- TVZRAEYQIKYCPH-UHFFFAOYSA-N 3-(trimethylsilyl)propane-1-sulfonic acid Chemical compound C[Si](C)(C)CCCS(O)(=O)=O TVZRAEYQIKYCPH-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- MEUKEBNAABNAEX-UHFFFAOYSA-N hydroperoxymethane Chemical compound COO MEUKEBNAABNAEX-UHFFFAOYSA-N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a high-efficiency Fe/ZSM-5 catalyst, and a preparation method and application thereof. The catalyst comprises an active component and a carrier, wherein the carrier is a ZSM-5 molecular sieve, and the active component is Fe in a mononuclear form 3+ Species, and which fall within the five-membered ring of ZSM-5 molecular sieve and replace
Description
Technical Field
The invention belongs to the technical field of catalytic oxidation, and particularly relates to a preparation method of a high-efficiency Fe/ZSM-5 catalyst and application of the high-efficiency Fe/ZSM-5 catalyst in preparation of acetic acid by low-temperature catalytic methane oxidative carbonylation.
Background
Methane is the smallest saturated hydrocarbon and is also the main component of natural gas, and is expected to become a potential carbon resource for replacing petroleum, so that the direct conversion of methane has great significance. Methane production sites are often remote from the area of use and transportation by pipeline construction can be costly. Thus, the conversion of methane to liquid products such as methanol, formic acid and acetic acid at the production site will greatly improve the difficult situation where methane is difficult to transport.
The methane molecule is composed of four equivalent C-H bonds, has a highly symmetrical regular tetrahedral structure, and has extremely stable thermodynamic properties. Due to the weak reactivity of methane, the current industrial application of preparing methanol from methane is mostly carried out in an indirect way: first, at high temperature [ ]>Under 800 ℃ conditions, methane is reformed into synthesis gas (CO/H) by reforming with water, oxygen or carbon dioxide 2 ) Then the synthesis gas is further converted into important basic chemical raw materials such as methanol, dimethyl ether, low-carbon mixed alcohol, low-carbon olefin and the like or synthetic liquid fuel under the condition of pressurization. The conversion of methane into synthesis gas is a thermodynamically favorable process, so that the carbon yield of the methanol prepared by indirect conversion of methane in industry is very high (about 70%), but the process has the defects of high energy consumption and complicated steps, and the high-efficiency utilization of methane is greatly limited. Compared with the traditional process for preparing the methanol by indirect conversion of methane, the process for preparing the oxygen-containing compounds such as the methanol, the formic acid, the acetic acid and the like by direct conversion of methane does not need to be subjected to a synthesis gas step, and has potential advantages in theory, such as mild reaction conditions, simple process and the like.
Acetic acid is an important chemical raw material and is mainly used for synthesizing vinyl acetate, acetic anhydride, acetate, terephthalic acid, ethanol and the like. The global market share of acetic acid in 2019 was $89.2 billion, with an annual growth rate between 2020-2027 estimated to be 5.2%. The apparent consumption of acetic acid in 2019 China is 626 ten thousand tons.
At present, the acetic acid synthesis in China mainly adopts a methanol carbonylation method, and most of domestic production devices adopt rhodium/iodine catalyst systems developed by Mengshan. The use of homogeneous rhodium-based catalysts, corrosive hydroiodic acid, and toxic methyl iodide in the reaction has disadvantages such as expensive catalyst, difficult catalyst recovery, the need to use special corrosion-resistant materials, and environmental potential risks.
Disclosure of Invention
The invention provides a preparation method and application of an Fe/ZSM-5 catalyst, wherein the catalyst is used for preparing acetic acid by catalyzing methane oxidative carbonylation at a low temperature and high efficiency, and has the advantages of high acetic acid yield, good stability, low price, convenient recovery and the like.
First, the invention provides a high-efficiency Fe/ZSM-5 catalyst, which comprises an active component and a carrier, wherein the carrier is a ZSM-5 molecular sieve, and the active component is Fe in a mononuclear form 3+ Species, and which fall within five-membered rings in ZSM-5 molecular sieve and replace
Protons in the acid position.
According to some embodiments of the catalyst of the invention, fe is present in mononuclear form 3+ The species account for more than 50% of the total Fe.
According to some embodiments of the catalyst of the present invention, the mass loading of Fe is 0.01wt% or less Fe/(molecular sieve+Fe) 2 O 3 ) Less than or equal to 10 weight percent. Preferably, the mass loading of Fe is 0.1wt% or less Fe/(molecular sieve+Fe) 2 O 3 ) Less than or equal to 1 weight percent. Preferably, the mass loading of Fe is 0.2wt% or less Fe/(molecular sieve+Fe) 2 O 3 ) Less than or equal to 0.75 weight percent. Preferably, the mass loading of Fe is 0.25wt% or less Fe/(molecular sieve+Fe) 2 O 3 ) Less than or equal to 0.5wt%, for example, 0.2wt% less than or equal to Fe/(molecular sieve+Fe) 2 O 3 )≤0.3wt％。
According to some embodiments of the catalyst of the present invention, the mole to silica ratio n (SiO 2 )/n(Al 2 O 3 )≥30。
According to some embodiments of the catalyst of the present invention, the mole to silica ratio n (SiO 2 )/n(Al 2 O 3 )≤100。
Preferably, the ZSM molecular sieve has a molar silica to alumina ratio n (SiO 2 )/n(Al 2 O 3 ) 30.
In addition, the invention provides a preparation method of the high-efficiency Fe/ZSM-5 catalyst, which comprises the following steps:
(1) Performing ion exchange on the ZSM-5 molecular sieve with the template removed in an ammonium salt solution to obtain NH 4 –ZSM-5；
(2) NH is added to 4 Performing vacuum pretreatment on the ZSM-5 molecular sieve;
(3) NH treated in step (2) 4 The ZSM-5 molecular sieve is impregnated with Fe salt solution,
(4) Drying and calcining the molecular sieve treated in the step (3).
According to some embodiments of the preparation method of the present invention, in step (1), the ammonium salt is ammonium nitrate at a concentration of 0.1 to 1.5mol·l -1 The ion exchange time is 12-48 hours; the temperature is 50-90 ℃.
According to some embodiments of the preparation method of the present invention, in step (2), the treatment time is not less than 0.5h and the treatment temperature is 20-40 ℃.
According to some embodiments of the preparation method of the present invention, in step (3), the Fe salt is selected from the group consisting of iron acetylacetonate, feCl 3 、Fe(NO 3 ) 3 Fe (b) 2 (SO 4 ) 3 The method comprises the steps of carrying out a first treatment on the surface of the The solvent in the Fe salt solution is a C1-C6 alcohol solvent (preferably ethanol) or a mixture of a C1-C6 alcohol solvent (preferably ethanol) and water.
According to some embodiments of the preparation method of the present invention, in step (3), the impregnation temperature is 20 to 40 ℃ and the impregnation time is 12 to 48 hours.
According to some embodiments of the preparation method of the present invention, in step (4), the drying mode is spin-drying, and the temperature of the spin-drying is 20-70 ℃.
According to some embodiments of the preparation process of the present invention, the ZSM-5 molecular sieve after removal of the templating agent is obtained by calcination, preferably at a calcination temperature of 300 to 800℃for a calcination time of 1 to 10 hours at a temperature increase rate of 0.1 to 5℃min -1 The calcination atmosphere is air, and the air flow is 0-50 mL.min -1 。
In addition, the invention also provides an application of the Fe/ZSM-5 catalyst or the Fe/ZSM-5 catalyst obtained by the preparation method in synthesizing acetic acid by methane carbonylation.
According to some embodiments of the inventive use, the feed gas used comprises methane and CO, and the oxidant used is a hydrogen peroxide solution.
According to some embodiments of the invention, the concentration of the hydrogen peroxide solution is 0.1-10 mol.L -1 Preferably 0.5 to 2 mol.L -1 。
According to some embodiments of the invention, the feed gas pressure is 1-20MPa, the higher the pressure, the better, and preferably 8MPa due to experimental conditions limitations.
According to some embodiments of the inventive use, the reaction temperature is between 0 and 100 ℃, preferably between 50 and 80 ℃.
According to some embodiments of the inventive use, the reaction time is from 0.5 to 10 hours, preferably from 0.5 to 2 hours.
According to some embodiments of the inventive use, the rotational speed is 500-1500rpm.
According to some embodiments of the inventive application, P CH4 /P CO =0.1-10, preferably 3/2.
According to some embodiments of the invention, the mass to volume ratio of catalyst to hydrogen peroxide solution is (10-100) mg/(1-20) mL.
The beneficial effects of the invention are as follows:
the catalyst provided by the invention can convert methane into acetic acid more efficiently and with high selectivity; can rapidly catalyze the reaction at a lower temperature; meanwhile, the catalyst has certain stability.
Drawings
FIG. 1 is a powder X-ray diffraction pattern of a ZSM-5, fe/ZSM-5 (0.05) of example 2, fe/ZSM-5 (0.1) of example 3, fe/ZSM-5 (0.25) of example 1, used-Fe/ZSM-5 (0.25) after reaction of example 1, and Fe/ZSM-5 (0.5) catalyst of example 4.
FIG. 2 is an ultraviolet-visible spectrum of the Fe/ZSM-5 (0.05) of example 2, the Fe/ZSM-5 (0.1) of example 3, the Fe/ZSM-5 (0.25) of example 1, and the Fe/ZSM-5 (0.5) catalyst of example 4.
FIG. 3 shows the relationship between Fe/ZSM-5 (molar silica alumina ratio 30) catalytic performance and single core Fe species for different loadings.
FIG. 4 is NH 4 ZSM-5 and Fe/ZSM-5 (0.25) catalysis of example 1Ultraviolet raman spectrum of the agent.
FIG. 5 shows ion fragments of the Fe/ZSM-5 catalyst of example 1 as measured by time of flight-secondary ion mass spectrometry (TOF-SIMS).
FIG. 6 is an ultraviolet visible spectrum of the used-Fe/ZSM-5 (0.25) catalyst (molar ratio 30) after the reaction of example 1.
Detailed Description
The following description of the embodiments of the present invention will be made with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. It should be noted that, without conflict, embodiments of the present invention and features in the embodiments may be combined with each other.
The catalyst system consists of NH 4 Fe-supported heterogeneous catalyst composition of ZSM-5 molecular sieve, wherein NH 4 ZSM-5 is prepared from ZSM-5 molecules through calcining to remove template and NH 4 NO 3 Solution (1 mol L) -1 ) Ion exchange (stirring time 12h; exchanging four times; the exchange temperature is 80 ℃ to remove sodium ions, wherein the ZSM molecular sieve has a molar silicon-aluminum ratio of SiO 2 /Al 2 O 3 ≥30。
The mode of introducing Fe into the catalyst is a vacuum impregnation method: NH is added to 4 Carrying out vacuumizing treatment on ZSM-5, wherein the treatment time is more than or equal to 0.5h; adding ferric acetylacetonate, fe (NO) 3 ) 3 Fe (b) 2 (SO 4 ) 3 The volume ratio of water to ethanol is 0-10; the dipping temperature is 20-40 ℃, the dipping time is 12-48h, and the stirring is 500-1500rpm; the impregnated material is calcined after spin-steaming and drying, wherein the Fe source is ethanol solution of ferric acetylacetonate, and the mass loading of Fe is less than or equal to 0.01wt% Fe/(molecular sieve+Fe) 2 O 3 )≤10wt％。
The calcination operations are all carried out in a muffle furnace, and the calcination temperature is 300 DEG CCalcining at-800 deg.C for 1-10 hr at a heating rate of 0.1-5 deg.C for min -1 The calcination atmosphere is air, and the air flow is 0-50mL min -1 。
Meanwhile, the invention also provides an application of the Fe/ZSM-5 catalyst obtained by the preparation method, wherein the Fe/ZSM-5 catalyst can be applied to methane oxidative carbonylation to synthesize a series of oxygen-containing compounds such as methanol, formic acid, acetic acid and the like, and the preparation method comprises the following specific steps: the reactivity of the methane oxidative carbonylation catalyst to acetic acid was evaluated in a 100mL autoclave. The reaction conditions are as follows: 10-100mg of catalyst, 1-20mL of catalyst, 0.1-10mol L -1 The hydrogen peroxide solution has a raw material gas pressure of 1-20MPa and a reaction temperature of 0-100 ℃.
Example 1
First, 20g of ZSM-5 molecular sieve raw powder (molar silicon-aluminum ratio n (SiO) 2 )/n(Al 2 O 3 ) =30), placed in a muffle furnace, and then air was introduced into the muffle furnace. Then at 1 ℃ for min -1 The heating rate of the molecular sieve is started to heat, the raw molecular sieve powder is calcined for 5 hours at 500 ℃, and then natural cooling is carried out, so that the Na-ZSM-5 molecular sieve without the template agent can be obtained. Adding 250mL of 1mol L of Na-ZSM-5 molecular sieve with template removed -1 NH of (C) 4 NO 3 The solution was then stirred at 500rpm for 12h at 80℃for ion exchange. Subsequently, the mixture was centrifuged at 4500rpm for 5min. After the centrifugation, the solution was washed with ultrapure water, and the solution was centrifuged and washed four times. After centrifugation four times 250mL of 1mol L were added -1 NH of (C) 4 NO 3 The solution was again subjected to the next ion exchange for a total of 4 ion exchanges. After the last centrifugation is finished, transferring the molecular sieve mud into a culture dish, drying in an oven at 80 ℃ for 10 hours, taking out the dried block, and grinding to obtain NH 4 -ZSM-5 molecular sieve powder. At room temperature, 0.016g of iron acetylacetonate was dissolved in a beaker containing 5mL of ethanol. Then, the ferric acetylacetonate solution was transferred to a reactor containing 1g of NH 4 In a flask of ZSM-5 molecular sieve, and it was previously evacuated for 30 minutes. The solution of ferric acetylacetonate remaining in the beaker was washed twice with 5mL of ultrapure water each, and the washed solution was also transferredMove into the flask described above. The mixture in the flask was stirred at room temperature for 24 hours. The impregnated catalyst was dried in a rotary evaporator at 70℃and calcined in a muffle furnace at 500℃for 3 hours to give a Fe/ZSM-5 (0.25) catalyst (mass loading of Fe: 0.25wt%, molar silica alumina ratio: 30).
30mg of the catalyst prepared and 10mL of 0.5mol L were weighed -1 The hydrogen peroxide solution was filled into a 100mL glass liner together with the magnetons, and then filled into a high-pressure reactor for sealing. The air inside the reaction kettle was replaced twice with 2MPa methane and 2MPa carbon monoxide in sequence. The tail gas is discharged to the outside along with the emptying pipeline. 2.5MPa methane and 2.5MPa carbon monoxide are filled into the reaction kettle, stirring is started at a rotating speed of 1500rpm, and the reaction kettle is heated to 50 ℃ for starting timing. After 0.5h the autoclave was placed in an ice-water bath for cooling for 30 minutes to reduce the loss of volatile products. The gaseous product was collected by air bag and TCD tested on GC 9790plus chromatograph. The residue in the reaction vessel was collected and centrifugally filtered to remove the catalyst from the liquid product. By passing through 1 The liquid product was quantified by H NMR. The nuclear magnetic measurement should be performed immediately after the liquid product is collected to prevent residual hydrogen peroxide from oxidizing the product to carbon dioxide. Typically, 0.4mL of filtered liquid reaction product and 0.1mL of D 2 O (containing 0.02wt% DSS) was packed into a liquid nuclear magnetic tube for measurement. In addition, the nuclear magnetic tube is covered by aluminum foil in the transfer process so as to prevent free radicals generated by decomposition of hydrogen peroxide by visible light, thereby oxidizing carbon-containing products. The evaluation results of the catalyst are shown in Table 1.
Example 2
The mass of the iron acetylacetonate used for the preparation of the catalyst was 0.0032g, and the other catalyst preparation steps were the same as in example 1, and the obtained catalyst was designated as: fe/ZSM-5 (0.05) (mass loading of Fe 0.05wt%, molar Si/Al ratio 30). The catalyst evaluation procedure and the reaction conditions were the same as in example 1, and the catalyst evaluation results are shown in Table 1.
Example 3
The mass of the iron acetylacetonate used for the preparation of the catalyst was 0.0064g, and the other catalyst preparation steps were the same as in example 1, and the catalyst obtained was designated as: fe/ZSM-5 (0.10) (mass loading of Fe: 0.10wt%, molar Si/Al ratio: 30). The catalyst evaluation procedure and the reaction conditions were the same as in example 1, and the catalyst evaluation results are shown in Table 1.
Example 4
The mass of the iron acetylacetonate used for the preparation of the catalyst was 0.0320g, and the other catalyst preparation steps were the same as in example 1, and the obtained catalyst was designated as: fe/ZSM-5 (0.50) (mass loading of Fe: 0.50wt%, molar Si/Al ratio: 30). The catalyst evaluation procedure and the reaction conditions were the same as in example 1, and the catalyst evaluation results are shown in Table 1.
Example 5
ZSM-5 molar ratio of silicon to aluminum n (SiO) used for preparing catalyst 2 )/n(Al 2 O 3 ) =60, other catalyst preparation steps were the same as in example 1, and the resulting catalyst was noted: fe/ZSM-5 (0.25; 60) (mass loading of Fe 0.25wt%, molar silica alumina ratio 60). The catalyst evaluation procedure and the reaction conditions were the same as in example 1, and the catalyst evaluation results are shown in Table 1.
Example 6
ZSM-5 molar ratio of silicon to aluminum n (SiO) used for preparing catalyst 2 )/n(Al 2 O 3 ) =130, other catalyst preparation steps were the same as in example 1, the resulting catalyst was noted: fe/ZSM-5 (0.25; 130) (mass loading of Fe 0.25wt%, molar silica alumina ratio 130). The catalyst evaluation procedure and the reaction conditions were the same as in example 1, and the catalyst evaluation results are shown in Table 1.
Example 7
ZSM-5 molar ratio of silicon to aluminum n (SiO) used for preparing catalyst 2 )/n(Al 2 O 3 ) =300, other catalyst preparation steps were the same as in example 1, and the resulting catalyst was noted: fe/ZSM-5 (0.25; 300) (mass loading of Fe 0.25wt%, molar Si/Al ratio 300). The catalyst evaluation procedure and the reaction conditions were the same as in example 1, and the catalyst evaluation results are shown in Table 1.
Comparative example 1
The ZSM-5 used for the preparation of the catalyst consisted entirely of silica, and the other catalyst preparation steps were the same as in example 1, the catalyst obtained being noted: fe/ZSM-5 (0.25;. Infinity.). The catalyst evaluation procedure and the reaction conditions were the same as in example 1, and the catalyst evaluation results are shown in Table 1.
Example 8
The catalyst preparation step and conditions were the same as in example 1, except that the reaction conditions in the catalyst evaluation step were changed to: 4MPa methane and 4MPa carbon monoxide.
Table 1: and (3) the catalysis evaluation results of the Fe/ZSM-5 catalysts with different Fe loading amounts and different silicon-aluminum ratios.
Example 9
The solid-liquid mixture after the reaction in example 1 was collected in a 100mL glass liner, dried at 120 ℃ for 12 hours to remove the liquid product, and the catalytic reaction was repeated. The fresh catalyst was not added, and the other steps and reaction conditions were the same as in example 1, and after repeating the above steps 4 times, the catalyst evaluation results are shown in table 2.
Table 2: fe/ZSM-5 (0.25; 30) catalyst stability test.
As is found by powder X-ray diffraction characterization of FIG. 1, fe is not observed 2 O 3 The diffraction peaks of (2) indicate that Fe is highly dispersed on the molecular sieve support and the particle size is below the detection limit (about 4 nm). Characterization of the ultraviolet visible spectrum of FIG. 2 shows that Fe has four existing forms, namely single-core four-coordination Fe 3+ Species (220-237 nm), mononuclear hexacoordinated Fe 3+ (267–289nm)，Fe x O y Clusters (353-368 nm) and Fe 2 O 3 Nano particles [ ]>500 nm). Analysis of the catalytic data obtained in examples 1,2,3,4 revealed that the yields of oxidation products (acetic acid, formic acid, methanol, and methyl hydroperoxide) were comparable to mononuclear hexacoordinated Fe 3+ The content of the species has a linear relationship and the selectivity of acetic acid and mononuclear four-coordinated Fe 3+ The proportions of the species also have a linear relationship, illustrating the catalyst in the present inventionIs a uniformly dispersed mononuclear Fe 3+ The species is shown in FIG. 3. The Fe species was located in five-membered rings in the ZSM-5 molecular sieve and replaced by those characterized by the UV Raman spectrum of FIG. 4
Protons in the acid position. Analysis of the catalytic data obtained in examples 1,5,6, and 7, as well as time-of-flight secondary ion mass spectrometry (ToF-SIMS) characterization of fig. 5, revealed that the activity of the mononuclear Fe sites was also closely related to the Al element in the ZSM-5 molecular sieve framework.
The catalyst obtained by the preparation method can effectively convert methane into acetic acid, the optimal reaction temperature is 50 ℃, and the catalyst has the advantages of low cost and high activity. In example 8, 10mL of the solution were subjected to 0.5mol L at 8MPa and 50 ℃ -1 Hydrogen peroxide, 30mg of Fe/ZSM-5 (the mass loading of Fe is 0.25wt percent, the mol ratio of silicon to aluminum is 30), ferric salt reagent is ferric acetylacetonate, the calcining temperature of the catalyst is 500 ℃, and P CH4 /P CO At 0.5h, 1500rpm, acetic acid space-time yield up to 12.01mmol g cat -1 h -1 Acetic acid selectivity was 63.24%. The comparison document 1 (Fe binuclear sites convert methane to acetic acid with ultrahigh selectivity, bo Wu et al, (Chem) volume 8, pages 1658-1672, month 3 and 2 of 2022, details of the preparation are given in page 10, synthesis of catalysts) discloses, as the closest prior art, a Fe-BN/ZSM-5 (BN is an abbreviation for dinuclear word, representing binuclear Fe as active site) catalyst prepared by vacuum impregnation, whose iron salt reagent used for the catalyst synthesis is FeCl 3 ·6H 2 O, catalyst calcination temperature 400 ℃, acetic acid space time yield 0.20mmol g cat -1 ·h -1 Acetic acid selectivity was 57%. Unlike the above documents, the present invention uses ferric acetylacetonate as an iron source, wherein three acetylacetonate molecules are wrapped around each iron atom, which is helpful for forming physical barriers between the iron atoms, and achieving the purpose of high dispersion; in addition, the calcination temperature used in the present invention is 500 ℃, which facilitates comparison of the document for iron species at high temperaturesThe experimental procedure in 1 was repeated and the results are found in comparative example 2.
Comparative example 2
At room temperature, 0.072g FeCl 3 ·6H 2 O was dissolved in a beaker containing 15mL of ultrapure water. Then, the ferric acetylacetonate solution was transferred to a reactor containing 1g of NH 4 In a flask of ZSM-5 molecular sieve, and it was previously evacuated for 30 minutes. The mixture in the flask was stirred at room temperature overnight. The impregnated catalyst was dried in an oven at 100deg.C and calcined in a muffle furnace at 400deg.C for 4 hours to give Fe-BN/ZSM-5 catalyst. The catalyst evaluation procedure and the reaction conditions were the same as in example 1, and the catalyst evaluation results are shown in Table 1.
Characterization by comparing Fe/ZSM-5 (0.25) catalyst (FIGS. 1 and 6) before and after the reaction, the ZSM-5 molecular sieve carrier and the mononuclear Fe were found 3+ The number of species is well maintained, and the main loss is inactive Fe x O y The stability of the Fe/ZSM-5 (0.25) catalyst of the invention was thus well maintained and verified in example 9.
The above embodiments are only for illustrating the present invention, and are not limiting of the present invention. While the invention has been described in detail with reference to the embodiments, those skilled in the art will appreciate that various combinations, modifications, or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and it is intended to be covered by the scope of the claims of the present invention.
Claims (10)
1. A high-efficiency Fe/ZSM-5 catalyst comprises an active component and a carrier, wherein the carrier is a ZSM-5 molecular sieve, and the active component is Fe in a mononuclear form 3+ Species, and which fall within the five-membered ring of ZSM-5 molecular sieve and replace
Protons in the acid position.
2. The catalyst according to claim 1A catalyst characterized by comprising Fe in the form of a single nucleus 3+ Species account for more than 50% of the total Fe; the mass loading of Fe is 0.01wt% or less Fe/(molecular sieve+Fe) 2 O 3 ) Less than or equal to 10wt%, preferably 0.25wt% or less Fe/(molecular sieve+Fe) 2 O 3 )≤0.5wt％。
3. A preparation method of a high-efficiency Fe/ZSM-5 catalyst comprises the following steps:
(1) Ion exchange is carried out on ZSM-5 molecular sieve after template agent removal in ammonium salt solution to prepare NH 4 –ZSM-5；
(2) NH is added to 4 Performing vacuum pretreatment on the ZSM-5 molecular sieve;
(3) NH treated in step (2) 4 -impregnating the ZSM-5 molecular sieve with a Fe salt solution;
(4) Drying and calcining the molecular sieve treated in the step (3), wherein the drying mode is rotary evaporation drying.
4. The process according to claim 3, wherein the ammonium salt in the step (1) is ammonium nitrate in a concentration of 0.1 to 0.5 mol.L -1 The ion exchange time is 12-48 hours; the temperature is 50-90 ℃; molar silicon-aluminum ratio n (SiO) of ZSM molecular sieve 2 )/n(Al 2 O 3 )≥30。
5. The process according to claim 3, wherein in step (2), the treatment time is not less than 0.5 hours and the treatment temperature is 20 to 40 ℃.
6. The process according to claim 3, wherein in the step (3), the Fe salt is selected from the group consisting of iron acetylacetonate and FeCl 3 、Fe(NO 3 ) 3 Fe (b) 2 (SO 4 ) 3 The method comprises the steps of carrying out a first treatment on the surface of the The solvent in the Fe salt solution is a C1-C6 alcohol solvent (preferably ethanol) or a mixture of a C1-C6 alcohol solvent (preferably ethanol) and water; the soaking temperature is 20-40 ℃ and the soaking time is 12-48h.
7. The process according to any one of claims 3 to 6, wherein in step (4), the spin drying temperature is 20 to 70 ℃.
8. The process according to any one of claims 3 to 7, wherein the ZSM-5 molecular sieve after removal of the template is obtained by calcination, preferably at a calcination temperature of 300 to 800 ℃, for a calcination time of 1 to 10 hours, at a temperature increase rate of 0.1 to 5 ℃ min -1 The calcination atmosphere is air, and the air flow is 0-50 mL.min -1 。
9. Use of the Fe/ZSM-5 catalyst according to any of claims 1-2 or the Fe/ZSM-5 catalyst obtained by the preparation process according to any of claims 3-8 in the oxidative carbonylation of methane to acetic acid.
10. The use according to claim 9, characterized in that the feed gas used comprises methane and CO and the oxidant used is a hydrogen peroxide solution; the concentration of the hydrogen peroxide solution is 0.1-10mol.L -1 Preferably 0.5 to 2mol L -1 The method comprises the steps of carrying out a first treatment on the surface of the The pressure of the raw material gas is 1-20MPa, preferably 2-8MPa; the reaction temperature is 0-100 ℃, preferably 25-75 ℃; the reaction time is 0.5-10h, preferably 0.5-2h; the rotation speed is 500-2000rpm, P CH4 /P CO =0.1-10, preferably 3/2; the mass volume ratio of the catalyst to the hydrogen peroxide solution is (10-100) mg/(1-20) mL.
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| BO WU ET AL: "《Fe binuclear sites convert methane to acetic acid with ultrahigh selectivity》", 《CHEM》, vol. 8, 9 June 2022 (2022-06-09), pages 1661 * |
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