CN115806479A - Conversion of CH 4 And CO 2 Method for directly preparing acetic acid - Google Patents
Conversion of CH 4 And CO 2 Method for directly preparing acetic acid Download PDFInfo
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- CN115806479A CN115806479A CN202211448164.1A CN202211448164A CN115806479A CN 115806479 A CN115806479 A CN 115806479A CN 202211448164 A CN202211448164 A CN 202211448164A CN 115806479 A CN115806479 A CN 115806479A
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- acetic acid
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- nitrate
- boric acid
- alumina
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 title claims abstract description 159
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 66
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 16
- 150000003624 transition metals Chemical class 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 23
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 22
- 239000004327 boric acid Substances 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 12
- 229920002472 Starch Polymers 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 230000004888 barrier function Effects 0.000 claims description 10
- 239000008107 starch Substances 0.000 claims description 10
- 235000019698 starch Nutrition 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000004898 kneading Methods 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 8
- 239000006229 carbon black Substances 0.000 claims description 7
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 239000001913 cellulose Substances 0.000 claims description 5
- 229920002678 cellulose Polymers 0.000 claims description 5
- 239000001307 helium Substances 0.000 claims description 5
- 229910052734 helium Inorganic materials 0.000 claims description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 8
- 230000003213 activating effect Effects 0.000 abstract 1
- 238000007654 immersion Methods 0.000 abstract 1
- 230000007704 transition Effects 0.000 abstract 1
- 239000011521 glass Substances 0.000 description 24
- 238000005303 weighing Methods 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 9
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- 238000002360 preparation method Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 241000282326 Felis catus Species 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910020639 Co-Al Inorganic materials 0.000 description 2
- 229910020675 Co—Al Inorganic materials 0.000 description 2
- 229910017767 Cu—Al Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910003310 Ni-Al Inorganic materials 0.000 description 2
- 229910007570 Zn-Al Inorganic materials 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- ZDGGJQMSELMHLK-UHFFFAOYSA-N m-Trifluoromethylhippuric acid Chemical compound OC(=O)CNC(=O)C1=CC=CC(C(F)(F)F)=C1 ZDGGJQMSELMHLK-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000013064 chemical raw material Substances 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
- 238000004939 coking Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- 238000012546 transfer Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates toAnd a process for converting CH 4 And CO 2 A process for directly preparing acetic acid includes such steps as preparing a macroreticular alumina carrier, preparing the transition metal-carried macroreticular alumina catalyst by immersion method for activating CH by plasma 4 And CO 2 Directly generating acetic acid for reaction. The method realizes the reaction of CH under the conditions of normal temperature and normal pressure 4 And CO 2 Converted into acetic acid with high added value, and avoids the traditional CH 4 And CO 2 The reaction requires harsh requirements such as high temperature and high pressure, and the macroporous alumina supported transition metal single-atom catalyst has good acetic acid selectivity and stability.
Description
Technical Field
The invention relates to the technical field of catalyst preparation, and relates to a method for converting CH 4 And CO 2 A method for directly preparing acetic acid; in particular to a preparation method and application of a transition metal monatomic catalyst loaded on macroporous alumina.
Background
CH 4 And CO 2 The direct reaction to generate the acetic acid is an atom economic reaction, can produce valuable chemical products, and has very important significance for reducing the greenhouse effect. In industry, acetic acid is an important organic chemical raw material, is widely used in the technical processes of synthetic fibers, medicines, pesticides and the like, and is an important component of the solid economy in China. The preparation method of the acetic acid comprises a method for preparing acetic acid by ethanol oxidation, a method for methanol carbonylation, a method for liquid-phase oxidation of low-carbon alkane, a method for oxidizing acetaldehyde, a method for oxidizing ethylene and the like. However, these preparation processes usually require noble metals as catalysts, and the reaction is usually carried out in more than two steps, which undoubtedly increases the cost of the process.
Scientists at home and abroad to CH 4 And CO 2 The subject of direct conversion to acetic acid has been studied, for example, huangwei et al, tai Yun Chi university, uses a two-step conversion technique to catalytically convert CH 4 And CO 2 Acetic acid was prepared by using Cu/Co bimetallic based catalyst (Journal of Catalysis,2001,201, 100), pd/C and Pt/Al 2 O 3 Catalyst (Catalysis Today,2003,88, 83), pd/SiO 2 And Rh/SiO 2 Catalyst (Fuel Processing Technology,2007,88, 319) to activate CH 4 And CO 2 . However, since the two-step process is a batch process, loading, unloading and separation are complicated, resulting in low selectivity of acetic acid, and the preparation process is often carried out at a temperature of 200 to 500 ℃, the catalyst is prone to carbon deposition and deactivation, and the generated acetic acid is also decomposed at a high temperature. In order to solve the problems, the CH is catalyzed by adopting a plasma technology 4 And CO 2 The preparation of acetic acid has significant advantages.
There is currently open literature investigating the use of plasma for CH 4 And CO 2 Co-conversion to high value chemical products, e.g. using Fe/SiO by Li et al 2 And Co/SiO 2 As catalyst, CH is catalyzed by dielectric barrier discharge plasma 4 And CO 2 Liquid products are produced with oxygenate selectivity of up to 40%, including acetic acid and alcohols. Through comparison of selectivity of different products, fe/SiO 2 The catalyst is favorable for CH 4 And CO 2 Formation of ethanol, co/SiO 2 The acid products and the long-chain alkane are favorably generated. (Applied Catalysis B: environmental,2020,261, 118228).
In CH 4 And CO 2 In the conversion and utilization process, most of the used catalysts are supported catalysts, and the service performance of the supported catalysts is often determined by the carriers; because the carrier determines the dispersion state of the active metal in the catalyst, the acid property of the catalyst, the mass transfer process in the catalyst particles, the strength of the catalyst and the like. The typical carrier, alumina, has been proved by a large number of experimental studies, and the alumina can effectively promote the dispersion of the active metals. At the same time, because of the presence of some hydroxyl groups and exposed aluminum atoms on the surface of the alumina, it exhibits the characteristics of B and L acids, and this surface acidity promotes the catalytic action of the alumina itself on the cracking of hydrocarbons to form acid products. The alumina with different apertures can be obtained by different preparation methods, wherein the catalyst prepared by taking the macroporous alumina as a carrier can effectively reduce coking and avoid activity reduction or inactivation caused by deposition of metal impurities, thereby prolonging the useAnd (4) service life.
For the supported metal catalyst, the efficiency of the single-atom catalysis with each metal atom as an active site is greatly improved, and the metal utilization efficiency of the traditional supported metal catalyst is far lower than the ideal level. Therefore, in order to maximize the catalytic efficiency of the metal and reduce the production cost, the preparation of a monatomic metal catalyst is the primary choice of researchers. The superior catalytic performance of monatomic catalysts comes from the many new properties that arise when the particle dispersion reaches the monatomic size, such as sharply increased surface free energy, quantum size effects, unsaturated coordination environments, and metal-support interactions.
Disclosure of Invention
The invention aims to improve the defects of the prior art and provide a method for converting CH 4 And CO 2 A process for directly preparing acetic acid from the macroporous alumina as the load of transition metal as single-atom catalyst used to catalyze CH under plasma at ordinary temp and pressure 4 And CO 2 Acetic acid is prepared.
The technical scheme of the invention is as follows: conversion of CH 4 And CO 2 The method for directly preparing the acetic acid comprises the following specific steps:
a) Preparing a transition metal single-atom catalyst loaded on macroporous alumina;
(1) Uniformly mixing an alumina precursor and a pore-expanding agent to obtain a mixture, then preparing a boric acid solution, adding the boric acid solution into the mixture, kneading and molding, and drying and roasting to obtain a macroporous alumina carrier;
(2) Dissolving metal nitrate, then adding the macroporous alumina carrier obtained in the step (1), and stirring at room temperature;
(3) Filtering, washing and drying the solution obtained in the step (2), and then roasting and reacting the solution in a protective atmosphere to obtain the macroporous alumina supported transition metal monatomic catalyst marked as SAs-M-Al 2 O 3 。
B) Production of acetic acid
Filling the catalyst prepared in the step A into a dielectric barrier discharge region, and setting the length of the discharge region and the size of a discharge gap of the reactor; then CH4 and CO2 gas are introduced, and the power voltage and the discharge frequency are adjusted to prepare the acetic acid.
Preferably, the alumina precursor in the step A (1) is one of titanium-containing pseudo-boehmite, zirconium-containing pseudo-boehmite or phosphorus-containing pseudo-boehmite; the pore-expanding agent is one or a mixture of two of carbon black, cellulose and starch; the boric acid solution is a boric acid aqueous solution or a boric acid-strong acid mixed aqueous solution, wherein the strong acid is one of nitric acid, phosphoric acid and hydrochloric acid; the mass ratio of the boric acid, the strong acid and the deionized water in the boric acid solution is 1 (0-1) to (4-10).
Preferably, the adding mass of the pore-expanding agent in the step A (1) is 3.0-10.0% of the mass of the alumina precursor; the adding mass of the boric acid solution is 3.0-20.0% of the mass of the alumina precursor; the drying temperature is 90-150 ℃, and the drying time is 4-5 h; the roasting temperature is 400-900 ℃, the heating rate is 2-8 ℃/min, and the roasting time is 2-4 h.
Preferably, the metal nitrate in the step A (2) is one of ferric nitrate, cupric nitrate, nickel nitrate, cobalt nitrate, zinc nitrate or indium nitrate; the mass ratio of the metal nitrate to the macroporous alumina carrier is 1 (6-20); the stirring time is 8-24 h.
Preferably, the drying temperature in the step A (3) is 80-150 ℃, and the drying time is 5-10 h; the protective atmosphere is one of hydrogen, argon or helium, and the flow rate of the gas is 10-60 mL/min; the temperature of the roasting reaction is 200-900 ℃, the heating rate is 4-10 ℃/min, and the reaction time is 2-5 h.
Preferably, the length of a discharge area of the reactor in the step B is 45-60 mm, and a discharge gap is 4-8 mm; introducing CO at normal temperature and normal pressure 2 And CH 4 The molar ratio of (0.2-2) to (1); the dosage of the catalyst is that the ratio of the mass of the catalyst to the volume of a discharge area is 0.8-2 g/cm 3 (ii) a The power supply voltage is 10-40V, and the discharge frequency is 9-15 kHz.
Has the beneficial effects that:
the macroporous alumina supported transition metal monatomic catalyst provided by the invention can be used in combination with plasma technologyCatalysis of CO at normal temperature and pressure 2 And CH 4 Directly converts to prepare acetic acid and has good catalytic activity and acetic acid selectivity.
Detailed Description
The present invention is described in more detail below with reference to examples. These examples are only illustrative of the best mode of carrying out the invention and do not limit the scope of the invention in any way.
Example 1
Step 1, weighing 300g of titanium-containing pseudo-boehmite, weighing 15g of carbon black and 10g of starch, and grinding to uniformly mix the carbon black and the starch to obtain a mixture. Dissolving 2g of boric acid and 1g of phosphoric acid by using 8mL of deionized water, adding the boric acid-strong acid mixed aqueous solution into the mixture, kneading uniformly to form a plastic body, drying at 110 ℃ for 4h, heating the obtained solid to 800 ℃ at the heating rate of 5 ℃/min, and preserving heat for 2h to obtain the macroporous alumina carrier.
And step 2, weighing 1.0145g of ferric nitrate and 6.0870g of the alumina carrier obtained in the step 1, dissolving, stirring for 8 hours at room temperature, filtering, washing and drying in an oven at 80 ℃ for 10 hours. And reacting the dried sample for 2 hours under the protection of hydrogen, wherein the hydrogen flow rate is 10mL/min, the reaction temperature is 540 ℃, and the heating rate is 5 ℃/min. Obtaining CO under the normal temperature plasma 2 And CH 4 Macroporous alumina supported iron monatomic catalyst for preparing acetic acid by conversion, and obtained catalyst is marked as SAs-Fe-Al 2 O 3 。
Example 2
Step 1, weighing 300g of zirconium-containing pseudo-boehmite, then weighing 18g of carbon black and 10g of starch, and grinding to uniformly mix the materials to obtain a mixture. Dissolving 10g of boric acid in 50mL of deionized water, adding the aqueous solution of the boric acid into the mixture, kneading uniformly to form a plastic body, drying at 100 ℃ for 5h, heating the obtained solid to 500 ℃ at the heating rate of 3 ℃/min, and preserving heat for 3h to obtain the macroporous alumina carrier.
And 2, weighing 0.8941g of copper nitrate and 7.1528g of the alumina carrier prepared in the step 1, dissolving, stirring for 13 hours at room temperature, filtering, washing, and drying in an oven at 90 ℃ for 7 hours. Drying the sample in heliumThe reaction is carried out for 3h under protection, the flow rate of helium gas is 15mL/min, the reaction temperature is 400 ℃, and the heating rate is 6 ℃/min. Obtaining CO under the normal temperature plasma 2 And CH 4 Macroporous alumina loaded copper monatomic catalyst for preparing acetic acid by conversion, and obtained catalyst is marked as SAs-Cu-Al 2 O 3 。
Example 3
Step 1, weighing 350g of pseudo-boehmite containing phosphorus, then weighing 13g of carbon black, and grinding to uniformly mix the materials to obtain a mixture. Dissolving 6g of boric acid and 2g of nitric acid by using 60mL of deionized water, adding the boric acid-strong acid mixed aqueous solution into the mixture, kneading uniformly to form a plastic body, drying at 120 ℃ for 4h, heating the obtained solid to 450 ℃ at the heating rate of 2 ℃/min, and preserving heat for 4h to obtain the macroporous alumina carrier.
And 2, weighing 1.4670g of nickel nitrate and 20.5380g of the alumina carrier prepared in the step 1, dissolving, stirring for 17 hours at room temperature, filtering, washing, and drying in an oven at 110 ℃ for 10 hours. And reacting the dried sample for 5 hours under the protection of argon, wherein the flow rate of the argon is 20mL/min, the reaction temperature is 450 ℃, and the heating rate is 4 ℃/min. Obtaining CO under the normal temperature plasma 2 And CH 4 Macroporous alumina supported nickel monatomic catalyst for preparing acetic acid by conversion, and obtained catalyst is marked as SAs-Ni-Al 2 O 3 。
Example 4
Step 1, 400g of titanium-containing pseudo-boehmite is weighed, 26g of carbon black and 14g of cellulose are weighed, and the mixture is obtained by grinding and uniformly mixing the materials. Dissolving 10g of boric acid and 5g of nitric acid by using 60mL of deionized water, adding the boric acid-strong acid mixed aqueous solution into the mixture, kneading uniformly to form a plastic body, drying at 120 ℃ for 4h, heating the obtained solid to 700 ℃ at the heating rate of 8 ℃/min, and preserving heat for 2h to obtain the macroporous alumina carrier.
And 2, weighing 0.9771g of cobalt nitrate and 17.1450g of the alumina carrier prepared in the step 1, dissolving, stirring for 24 hours at room temperature, filtering, washing, and drying in an oven at 120 ℃ for 5 hours. Reacting the dried sample for 2 hours under the protection of hydrogen, wherein the hydrogen flow rate is 40mL/min, the reaction temperature is 250 ℃, and the temperature rise rate is highThe rate was 10 ℃/min. Obtaining CO under the normal temperature plasma 2 And CH 4 Macroporous alumina supported cobalt single-atom catalyst for preparing acetic acid by conversion, and obtained catalyst is marked as SAs-Co-Al 2 O 3 。
Example 5
Step 1, weighing 340g of zirconium-containing pseudo-boehmite, then weighing 18g of starch and 10g of cellulose, and grinding to uniformly mix the starch and the cellulose to obtain a mixture. Dissolving 10g of boric acid and 4g of phosphoric acid by using 40mL of deionized water, adding the boric acid-strong acid mixed aqueous solution into the mixture, kneading uniformly to form a plastic body, drying at 140 ℃ for 4h, heating the obtained solid to 600 ℃ at the heating rate of 8 ℃/min, and preserving heat for 3h to obtain the macroporous alumina carrier.
And 2, weighing 1.7365g of zinc nitrate and 22.5745g of the alumina carrier prepared in the step 1, dissolving, stirring at room temperature for 12 hours, filtering, washing, and drying in an oven at 150 ℃ for 6 hours. And reacting the dried sample for 2h under the protection of helium gas, wherein the flow rate of the helium gas is 50mL/min, the reaction temperature is 900 ℃, and the heating rate is 6 ℃/min. Obtaining CO under the normal temperature plasma 2 And CH 4 Macroporous alumina loaded zinc monatomic catalyst for preparing acetic acid by conversion, and obtained catalyst is marked as SAs-Zn-Al 2 O 3 。
Example 6
Step 1, weighing 360g of titanium-containing pseudo-boehmite, weighing 25g of starch, and grinding to uniformly mix the starch and the starch to obtain a mixture. Dissolving 4g of boric acid and 1g of hydrochloric acid by using 40mL of deionized water, adding the boric acid-strong acid mixed aqueous solution into the mixture, kneading uniformly to form a plastic body, drying at 150 ℃ for 5h, heating the obtained solid to 720 ℃ at the heating rate of 7 ℃/min, and preserving heat for 2h to obtain the macroporous alumina carrier.
And 2, weighing 1.3108g of zinc nitrate and 25.5606g of the alumina carrier prepared in the step 1, dissolving, stirring at room temperature for 18 hours, filtering, washing, and drying in an oven at 110 ℃ for 5 hours. And (3) reacting the dried sample with the product under the protection of argon for 4 hours, wherein the flow rate of the argon is 15mL/min, the reaction temperature is 550 ℃, and the heating rate is 8 ℃/min. Obtaining CO under the normal temperature plasma 2 And CH 4 Large-pore alumina supported indium monatomic catalyst for preparing acetic acid by conversion, and obtained catalyst is marked as SAs-In-Al 2 O 3 。
Application example 1
The invention prepares a macroporous alumina-supported transition metal single-atom catalyst, and adopts plasma to catalyze CH 4 And CO 2 Directly preparing acetic acid. The plasma reactor consists of two coaxial cylindrical glass tubes, and water circulation is arranged between the outer side of the inner glass tube and the inner side of the outer glass tube and is used as a grounding electrode; the high voltage electrode of the reactor is arranged on the axis of the coaxial glass tube. The length of a discharge area of the reactor is 45mm, and a discharge gap is 5mm; 1.7g of SAs-Fe-Al 2 O 3 The catalyst (prepared in example 1) is filled in a dielectric barrier discharge region, and CO is introduced at normal temperature and normal pressure 2 And CH 4 The molar ratio of (1) was 0.2, the power supply input voltage was 15V, and the discharge frequency was 10.0kHz. Under the above conditions, the selectivity to acetic acid was 78.16%, and the space-time yield of acetic acid was 184 mmol/kg cat -1 ·h -1 。
Application example 2
The invention prepares a macroporous alumina-supported transition metal monoatomic catalyst, and adopts plasma to catalyze CH 4 And CO 2 Directly preparing acetic acid. The plasma reactor consists of two coaxial cylindrical glass tubes, and water circulation is arranged between the outer side of the inner glass tube and the inner side of the outer glass tube and is used as a grounding electrode; the high-voltage electrode of the reactor is arranged on the axis of the coaxial glass tube. The length of a discharge area of the reactor is 58mm, and a discharge gap is 6mm; 2.1g of SAs-Cu-Al 2 O 3 The catalyst (prepared in example 2) is filled in a dielectric barrier discharge region, and CO is introduced at normal temperature and normal pressure 2 And CH 4 The molar ratio of (1). Under the above conditions, the selectivity of acetic acid was 96.45%, and the space-time yield of acetic acid was 421 mmol/kg cat -1 ·h -1 。
Application example 3
The invention prepares a transition metal monoatomic catalyst loaded on macroporous alumina by adopting plasmaBulk catalytic CH 4 And CO 2 Directly preparing acetic acid. The plasma reactor consists of two coaxial cylindrical glass tubes, and water circulation is arranged between the outer side of the inner glass tube and the inner side of the outer glass tube and is used as a grounding electrode; the high voltage electrode of the reactor is arranged on the axis of the coaxial glass tube. The length of a discharge area of the reactor is 60mm, and a discharge gap is 6mm; 2g of SAs-Ni-Al 2 O 3 The catalyst (prepared in example 3) was filled in the dielectric barrier discharge region, and CO was introduced at normal temperature and pressure 2 And CH 4 The molar ratio of (1) was 0.8, the power supply input voltage was 20V, and the discharge frequency was 12.0kHz. Under the above conditions, the selectivity to acetic acid was 88.73%, and the space-time yield of acetic acid was 374 mmol/kg cat -1 ·h -1 。
Application example 4
The invention prepares a macroporous alumina-supported transition metal monoatomic catalyst, and adopts plasma to catalyze CH 4 And CO 2 Directly preparing acetic acid. The plasma reactor consists of two coaxial cylindrical glass tubes, and water circulation is arranged between the outer side of the inner glass tube and the inner side of the outer glass tube and is used as a grounding electrode; the high voltage electrode of the reactor is arranged on the axis of the coaxial glass tube. The length of a discharge area of the reactor is 60mm, and a discharge gap is 8mm; 3.8g of SAs-Co-Al 2 O 3 The catalyst (prepared in example 4) was filled in the dielectric barrier discharge region, and CO was introduced at normal temperature and pressure 2 And CH 4 1, the power supply input voltage is 25V, and the discharge frequency is 14.0kHz. Under the above conditions, the selectivity of acetic acid was 82.99%, and the space-time yield of acetic acid was 202 mmol/kg cat -1 ·h -1 。
Application example 5
The invention prepares a macroporous alumina-supported transition metal single-atom catalyst, and adopts plasma to catalyze CH 4 And CO 2 Directly preparing acetic acid. The plasma reactor consists of two coaxial cylindrical glass tubes, and water circulation is arranged between the outer side of the inner glass tube and the inner side of the outer glass tube and is used as a grounding electrode; the high voltage electrode of the reactor is arranged on the axis of the coaxial glass tube. The length of a discharge area of the reactor is 48mm, and a discharge gap is 8mm; 2.1gSAs-Zn-Al 2 O 3 The catalyst (prepared in example 5) was filled in a dielectric barrier discharge region, and CO was introduced at normal temperature and pressure 2 And CH 4 The molar ratio of (1.4). Under the above conditions, the selectivity of acetic acid was 90.40%, and the space-time yield of acetic acid was 386 mmol/kg cat -1 ·h -1 。
Application example 6
The invention prepares a macroporous alumina-supported transition metal single-atom catalyst, and adopts plasma to catalyze CH 4 And CO 2 Directly preparing acetic acid. The plasma reactor consists of two coaxial cylindrical glass tubes, and water circulation is arranged between the outer side of the inner glass tube and the inner side of the outer glass tube and is used as a grounding electrode; the high voltage electrode of the reactor is arranged on the axis of the coaxial glass tube. The length of a discharge area of the reactor is 48mm, and a discharge gap is 5mm; 2.6g of SAs-In-Al 2 O 3 The catalyst (prepared in example 6) was filled in the dielectric barrier discharge region, and CO was introduced at normal temperature and pressure 2 And CH 4 The molar ratio of (2). Under the above conditions, the selectivity to acetic acid was 84.67%, and the space-time yield of acetic acid was 268 mmol/kg cat -1 ·h -1 。
Comparative example 1
Wang et al used Cu/HZSM-5 as a catalyst and applied dielectric barrier discharge to react CO 2 And CH 4 Conversion to a chemical value product with 17.65% selectivity to acetic acid. (Applied Catalysis B: environmental 315 (2022) 121583)
Comparative example 2
Li et al prepared a series of nickel-based catalysts by using foamed nickel as carrier, and catalyzed CO by using plasma technology 2 And CH 4 Conversion to oxygenates with acetic acid selectivity of up to 18.08%. (Journal of CO) 2 Utilization 52(2021)101675)
Each SAs-M-Al 2 O 3 The results of the catalyst performance test are shown in table 1. As can be seen from the comparative examples, the catalyst and plasma technology are also being usedCatalytic CH 4 And CO 2 Under the condition of preparing acetic acid by conversion, the selectivity of the macroporous alumina supported transition metal monatomic catalyst prepared by the invention to the acetic acid is higher, which shows that the monatomic catalyst prepared by the invention has a good effect on the reaction.
TABLE 1 SAs-M-Al 2 O 3 Results of catalyst Performance test
Claims (6)
1. Conversion of CH 4 And CO 2 The method for directly preparing the acetic acid comprises the following specific steps:
a) Preparing a transition metal monoatomic catalyst loaded on macroporous alumina;
(1) Uniformly mixing an alumina precursor and a pore-expanding agent to obtain a mixture, then preparing a boric acid solution, adding the boric acid solution into the mixture, kneading and molding, and drying and roasting to obtain a macroporous alumina carrier;
(2) Dissolving metal nitrate, then adding the macroporous alumina carrier obtained in the step (1), and stirring;
(3) Filtering, washing and drying the solution obtained in the step (2), and then roasting and reacting the solution in a protective atmosphere to obtain the macroporous alumina supported transition metal single-atom catalyst marked as SAs-M-Al 2 O 3 ；
B) Production of acetic acid
Filling the macroporous alumina-supported transition metal monatomic catalyst prepared in the step A into a dielectric barrier discharge region, and setting the length of the discharge region and the size of a discharge gap of the reactor; then CH is introduced 4 And CO 2 And (3) gas, and adjusting the voltage of a power supply and the discharge frequency to prepare the acetic acid.
2. The method of claim 1, wherein the alumina precursor in step a (1) is one of titanium-containing pseudo-boehmite, zirconium-containing pseudo-boehmite, or phosphorus-containing pseudo-boehmite; the pore-expanding agent is one or a mixture of two of carbon black, cellulose and starch; the boric acid solution is a boric acid aqueous solution or a mixed aqueous solution of boric acid and strong acid, wherein the strong acid is one of nitric acid, phosphoric acid or hydrochloric acid; the mass ratio of the boric acid, the strong acid and the deionized water in the boric acid solution is 1 (0-1) to (4-10).
3. The method according to claim 1, wherein the pore-expanding agent added in step a (1) is 3.0-10.0% by mass of the alumina precursor; the adding mass of the boric acid solution is 3.0-20.0% of the mass of the alumina precursor; the drying temperature is 90-150 ℃, and the drying time is 4-5 h; the roasting temperature is 400-900 ℃, the heating rate is 2-8 ℃/min, and the roasting time is 2-4 h.
4. The method of claim 1, wherein: the metal nitrate in the step A (2) is one of ferric nitrate, cupric nitrate, nickel nitrate, cobalt nitrate, zinc nitrate or indium nitrate; the mass ratio of the metal nitrate to the macroporous alumina carrier is 1 (6-20); the stirring time is 8-24 h.
5. The method of claim 1, wherein: the drying temperature in the step A (3) is 80-150 ℃, and the drying time is 5-10 h; the protective atmosphere is one of hydrogen, argon or helium, and the flow rate of the gas is 10-60 mL/min; the temperature of the roasting reaction is 200-900 ℃, the heating rate is 4-10 ℃/min, and the reaction time is 2-5 h.
6. The method of claim 1, wherein: the length of a discharge area of the reactor in the step B is 45-60 mm, and a discharge gap is 4-8 mm; introduction of CO 2 And CH 4 The molar ratio of (0.2-2) to (1); the dosage of the catalyst is that the ratio of the filling quality of the catalyst to the volume of a discharge area is 0.8-2 g/cm 3 (ii) a The power voltage is 10-40V, and the discharge frequency is 9-15 kHz.
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