CN118206436A - Method for preparing cyclopentanone by oxidation of cyclopentane - Google Patents
Method for preparing cyclopentanone by oxidation of cyclopentane Download PDFInfo
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- CN118206436A CN118206436A CN202211617988.7A CN202211617988A CN118206436A CN 118206436 A CN118206436 A CN 118206436A CN 202211617988 A CN202211617988 A CN 202211617988A CN 118206436 A CN118206436 A CN 118206436A
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- cyclopentane
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- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 title claims abstract description 117
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 title claims abstract description 90
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 39
- 238000007254 oxidation reaction Methods 0.000 title claims description 17
- 230000003647 oxidation Effects 0.000 title claims description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- 239000002808 molecular sieve Substances 0.000 claims abstract description 21
- 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 21
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 21
- 150000003624 transition metals Chemical class 0.000 claims abstract description 20
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 claims abstract description 17
- 230000001590 oxidative effect Effects 0.000 claims abstract description 11
- 239000007800 oxidant agent Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 230000035484 reaction time Effects 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- 239000002904 solvent Substances 0.000 claims description 17
- 239000010936 titanium Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims 5
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract 1
- 238000011084 recovery Methods 0.000 abstract 1
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 description 12
- 229910001220 stainless steel Inorganic materials 0.000 description 9
- 239000010935 stainless steel Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 7
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- -1 carbon five Chemical compound 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- KVWWIYGFBYDJQC-UHFFFAOYSA-N methyl dihydrojasmonate Chemical compound CCCCCC1C(CC(=O)OC)CCC1=O KVWWIYGFBYDJQC-UHFFFAOYSA-N 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- JTHVYOIHZNYRCC-UHFFFAOYSA-N 2-hexylcyclopentan-1-one Chemical compound CCCCCCC1CCCC1=O JTHVYOIHZNYRCC-UHFFFAOYSA-N 0.000 description 1
- CFMZSMGAMPBRBE-UHFFFAOYSA-N 2-hydroxyisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(O)C(=O)C2=C1 CFMZSMGAMPBRBE-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-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
- 101150003085 Pdcl gene Proteins 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229940124599 anti-inflammatory drug Drugs 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 239000002246 antineoplastic agent Substances 0.000 description 1
- 229940041181 antineoplastic drug Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- XCIXKGXIYUWCLL-HOSYLAQJSA-N cyclopentanol Chemical group O[13CH]1CCCC1 XCIXKGXIYUWCLL-HOSYLAQJSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229920003240 metallophthalocyanine polymer Polymers 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides a method for preparing cyclopentanone by oxidizing cyclopentane. The method uses cyclopentane as a reactant, hydrogen peroxide as an oxidant, a titanium-silicon molecular sieve loaded by transition metal as a catalyst, and the reaction is carried out for 4 to 10 hours at the temperature of between 60 and 150 ℃ to obtain cyclopentanone. The cyclopentanone preparation method disclosed by the invention has the advantages of low-cost and easily-obtained raw materials, short reaction time, low energy consumption, simple post-treatment, easy separation and recovery of the catalyst and recycling. The conversion rate of the cyclopentane reaches more than 50%, the selectivity of the cyclopentanone reaches more than 90%, and the method has industrial application prospect.
Description
Technical Field
The invention relates to a method for preparing cyclopentanone by oxidation of cyclopentane, and belongs to the field of chemistry and chemical engineering.
Background
Cyclopentanone is an important intermediate in fine chemical industry, is one of the main raw materials of perfume and pharmaceutical industry, can be used for preparing novel perfume 2-n-hexyl cyclopentanone, methyl dihydrojasmonate, brandone and various anti-inflammatory and anticancer drugs, and can also be used for synthesizing pesticides and herbicides. In addition, since cyclopentanone has excellent solubility for various resins, high-purity cyclopentanone is widely used as a solvent in the electronics industry.
At present, the main synthesis methods of cyclopentanone mainly comprise the following three methods: adipic acid pyrolysis, cyclopentene oxidation and cyclopentanol catalytic dehydrogenation. Among them, adipic acid pyrolysis is the main method for cyclopentanone production, accounting for about more than 90% of the total world yield. The method has simple process, but adipic acid has higher price and generates a large amount of pollutants, which limits the further development of the process. The cyclopentene oxidation method is to oxidize olefin directly into ketone or aldehyde under homogeneous condition with PdCl 2 and CuCl 2 as catalyst and air or pure oxygen as oxygen source. The method has the advantages of complex catalyst synthesis, irrational reaction conversion rate and cyclopentanone selectivity, homogeneous catalytic system, difficult catalyst separation and some unsolved problems in process or engineering. In the process of preparing cyclopentanone by catalytic dehydrogenation of cyclopentanol, the yield of cyclopentanone is high, the reaction process is environment-friendly, but the source of cyclopentanol serving as a raw material in the method is always difficult, so that the industrial development of the process is limited.
Cyclopentane is an important component in the byproduct of cracking ethylene, namely carbon five, can be separated from a carbon five fraction, and can also be prepared by hydrogenating cyclopentadiene and cyclopentene in the carbon five fraction. Currently, cyclopentane is mainly used as a solvent and a foaming agent, and the added value is not high. The products of the catalytic oxidation of cyclopentane mainly comprise cyclopentanol and cyclopentanone, which are important intermediates of fine chemical products of medicines and pesticides. Therefore, the downstream high-added value product of cyclopentane is developed through oxidation reaction, and the cyclopentane has wide application prospect and is a current research hotspot.
For example, the paper "technical research on the preparation of cyclopentanol and cyclopentanone by oxidation of cyclopentane" (fine and special chemicals, volume 28, phase 3) reports a method for preparing cyclopentanol and cyclopentanone by oxidation of cyclopentane using low-cost cyclopentane as a raw material and titanium-silicon molecular sieve as a catalyst, but the conversion rate of cyclopentane is lower, the main product is cyclopentanol, and the selectivity of cyclopentanone is lower.
Chinese patent CN1025237355A discloses a method for preparing cyclopentanol and cyclopentanone by oxidation of cyclopentane, the method uses transition metal salt or oxide, metalloporphyrin, metallophthalocyanine, and N-hydroxyphthalimide as catalyst, uses oxygen-containing gas as oxidant, and synthesizes cyclopentanol and cyclopentanone by catalytic oxidation of cyclopentane, the conversion rate of cyclopentane is higher, and the total selectivity of oxidation products cyclopentanol and cyclopentanone is higher. The disadvantage is that the catalyst composition in this process is complex and the selectivity to cyclopentanone in the product is low.
Chinese patent CN104447261a discloses a process for preparing cyclopentanol and cyclopentanone from cyclopentane. The method takes cyclopentane as a raw material, oxygen as an oxidant, and adopts a supported gold catalyst to catalyze and oxidize the cyclopentane to synthesize cyclopentanol and cyclopentanone. The reaction is carried out for 3 to 6 hours at the reaction temperature of 150 ℃ and the pressure of 2.0Mpa, the conversion rate of the cyclopentane can reach 10.2 percent, and the selectivity of the cyclopentanol and the cyclopentanone is respectively 32.6 percent and 45.4 percent. The catalyst used in the method is a heterogeneous catalyst loaded with gold, the price is high, the conversion rate of cyclopentane is low, and the selectivity of cyclopentanone is less than 50%.
The oxidation of cyclopentane by oxidation catalysts with high activity to prepare cyclopentanone has not been reported so far.
Disclosure of Invention
The invention aims to solve the problems of low cyclopentane conversion rate, low cyclopentanone selectivity and the like in the prior art, and provides a method for preparing cyclopentanone by oxidizing cyclopentane.
According to one aspect of the present application, there is provided a process for preparing cyclopentanone by oxidation of cyclopentane, comprising the steps of:
the method comprises the steps of (1) contacting a raw material containing cyclopentane, an oxidant and a solvent with a catalyst, and reacting to obtain a product containing cyclopentanone;
Wherein the catalyst comprises a titanium silicalite molecular sieve and a transition metal supported on the surface of the titanium silicalite molecular sieve;
wherein the catalyst is a titanium silicalite molecular sieve supported by transition metal;
the transition metal is at least one of vanadium, manganese, iron, cobalt, nickel and copper;
in the catalyst, the mass content of the transition metal is 0.5-5 wt%;
in the catalyst, the molar ratio of silicon to titanium in the titanium-silicon molecular sieve is 30-100.
The oxidant comprises hydrogen peroxide;
The mass concentration of the hydrogen peroxide is 27.5-50wt%;
The molar ratio of the oxidant to the cyclopentane is 0.5-5.
The solvent comprises at least one of water, acetonitrile, acetone, methanol and tertiary amyl alcohol;
the mass ratio of the solvent to the cyclopentane is 0.1-10.
The mass ratio of the cyclopentane to the catalyst is (10-100): 1.
The temperature of the reaction is 60-150 ℃;
the reaction time is 4-10 h.
The catalyst is obtained through the following steps:
and (3) immersing the titanium-silicon molecular sieve in an aqueous solution containing a transition metal precursor, drying and roasting to obtain the catalyst.
The transition metal precursor comprises ammonium metavanadate and soluble nitrate of other transition metals;
In the aqueous solution containing the transition metal precursor, the mass concentration of the transition metal precursor is 1-5wt%;
The solid-to-liquid ratio of the titanium silicon molecular sieve to the aqueous solution containing the transition metal precursor is (10-50): 1g/ml.
The temperature of the impregnation is 30-80 ℃;
the soaking time is 2-6 h;
Stirring in the soaking process;
The drying temperature is 80-120 ℃;
The drying time is 12-20 h;
And (3) standing and drying the drying.
The roasting temperature is 450-600 ℃;
The roasting time is 2-8 h.
The application has the advantages that:
The method for preparing cyclopentanone by oxidation of cyclopentane has the advantages of cheap and easily obtained cyclopentane raw materials, easily separated and recovered catalyst, recycling, short reaction time, low energy consumption, simple post-treatment and the like, the conversion rate of cyclopentane can reach more than 50%, the selectivity of cyclopentanone reaches more than 90%, and the method is very suitable for industrial production.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Unless otherwise indicated, all starting materials in the examples of the present application were purchased commercially.
Comparative example 1
5G of cyclopentane and 5g of hydrogen peroxide (the mass concentration is 50%) are added into a 100mL stainless steel reaction kettle, methanol is used as a solvent, the addition amount of the methanol is 5g, no catalyst is added, and after stirring for 6 hours at the constant temperature of 80 ℃, the conversion rate of the cyclopentane is 0.5%, and the selectivity of the cyclopentanone is 1.2%.
Comparative example 2
5G of cyclopentane and 5g of hydrogen peroxide (the concentration is 50%) are added into a 100mL stainless steel reaction kettle, methanol is used as a solvent, the addition amount of the methanol is 5g, 0.2g of titanium-silicon molecular sieve (TS-1) is added, wherein the molar ratio of Si/Ti in the titanium-silicon molecular sieve is 30, and after stirring for 6 hours at a constant temperature of 80 ℃, the conversion rate of the cyclopentane is 15.8%, and the selectivity of the cyclopentanone is 5.6%.
Example 1
5G of cyclopentane and 5g of hydrogen peroxide (the concentration is 50%) are added into a 100mL stainless steel reaction kettle, methanol is taken as a solvent, the addition amount of the methanol is 5g, and 0.2g of Cu/TS-1 is added, wherein the molar ratio of Si/Ti in the titanium-silicon molecular sieve is 30, and the loading amount of Cu is 1.0 wt%. After stirring at constant temperature of 80℃for 6h, the conversion of cyclopentane was 55.8% and the selectivity of cyclopentanone was 91.6%.
Example 2
5G of cyclopentane and 5g of hydrogen peroxide (the concentration is 50%) are added into a 100mL stainless steel reaction kettle, methanol is used as a solvent, the addition amount of water is 1.0g, and 0.2g of Fe/TS-1 is added, wherein the molar ratio of Si/Ti in the titanium-silicon molecular sieve is 30, and the loading amount of Fe is 1.0 wt%. After stirring at 60℃for 6h at constant temperature, the conversion of cyclopentane was 52.5% and the selectivity of cyclopentanone was 90.2%.
Example 3
5G of cyclopentane and 5g of hydrogen peroxide (the concentration is 50%) are added into a 100mL stainless steel reaction kettle, methanol is used as a solvent, the addition amount of water is 1.0g, and 0.2g of Fe/TS-1 is added, wherein the molar ratio of Si/Ti in the titanium-silicon molecular sieve is 30, and the loading amount of Fe is 1.0 wt%. After stirring at a constant temperature of 150℃for 6 hours, the conversion of cyclopentane was 70.5% and the selectivity of cyclopentanone was 95.2%.
Example 4
5G of cyclopentane and 10g of hydrogen peroxide (the concentration is 50%) are added into a 100mL stainless steel reaction kettle, methanol is used as a solvent, the addition amount of tertiary butanol is 5.0g, and 0.2g of Co/TS-1 is added, wherein the molar ratio of Si/Ti in the titanium-silicon molecular sieve is 50, and the loading amount of Co is 5.0wt%. After stirring at a constant temperature of 100℃for 6 hours, the conversion of cyclopentane was 60.5% and the selectivity of cyclopentanone was 93.8%.
Example 5
5G of cyclopentane and 10g of hydrogen peroxide (with the concentration of 27.5%) are added into a 100mL stainless steel reaction kettle, methanol is used as a solvent, the addition amount of acetone is 5.0g, and 0.2g of Ni/TS-1 is added, wherein the molar ratio of Si/Ti in the titanium-silicon molecular sieve is 70, and the loading amount of Ni is 3.0wt.%. After stirring at a constant temperature of 100℃for 10 hours, the conversion of cyclopentane was 57.8% and the selectivity of cyclopentanone was 91.4%.
Example 6
5G of cyclopentane and 10g of hydrogen peroxide (with the concentration of 27.5%) are added into a 100mL stainless steel reaction kettle, methanol is used as a solvent, the addition amount of acetonitrile is 5.0g, 0.5g V/TS-1 is added, wherein the molar ratio of Si/Ti in the titanium-silicon molecular sieve is 30, and the load of V is 3.0 wt%. After stirring at a constant temperature of 100℃for 10 hours, the conversion of cyclopentane was 67.8% and the selectivity of cyclopentanone was 95.4%.
Example 7
5G of cyclopentane, 15g of hydrogen peroxide (the concentration is 50%) and methanol as a solvent are added into a 100mL stainless steel reaction kettle, the addition amount of acetone is 5.0g, and 0.5g of Mn/TS-1 is added, wherein the molar ratio of Si/Ti in the titanium-silicon molecular sieve is 30, and the loading amount of Mn is 0.5 wt%. After stirring at 150℃for 6h at constant temperature, the conversion of cyclopentane was 57.8% and the selectivity of cyclopentanone was 92.4%.
While the application has been described in terms of preferred embodiments, it will be understood by those skilled in the art that various changes and modifications can be made without departing from the scope of the application, and it is intended that the application is not limited to the specific embodiments disclosed.
Claims (8)
1. A method for preparing cyclopentanone by oxidation of cyclopentane is characterized in that,
The method comprises the following steps:
the method comprises the steps of (1) contacting a raw material containing cyclopentane, an oxidant and a solvent with a catalyst, and reacting to obtain a product containing cyclopentanone;
wherein the catalyst is a titanium silicalite molecular sieve supported by transition metal;
the transition metal is at least one of vanadium, manganese, iron, cobalt, nickel and copper;
in the catalyst, the mass content of the transition metal is 0.5-5 wt%;
in the catalyst, the molar ratio of silicon to titanium in the titanium-silicon molecular sieve is 30-100.
2. The method of claim 1, wherein the step of determining the position of the substrate comprises,
The oxidant is hydrogen peroxide;
The mass concentration of the hydrogen peroxide is 27.5-50wt%;
The molar ratio of the oxidant to the cyclopentane is 0.5-5.
3. The method of claim 1, wherein the step of determining the position of the substrate comprises,
The solvent comprises at least one of water, acetonitrile, acetone, methanol and tertiary amyl alcohol;
the mass ratio of the solvent to the cyclopentane is 0.1-10.
4. The method of claim 1, wherein the step of determining the position of the substrate comprises,
The mass ratio of the cyclopentane to the catalyst is (10-100): 1.
5. The method of claim 1, wherein the step of determining the position of the substrate comprises,
The temperature of the reaction is 60-150 ℃;
the reaction time is 4-10 h.
6. The method of claim 1, wherein the step of determining the position of the substrate comprises,
The catalyst is obtained through the following steps:
and (3) immersing the titanium-silicon molecular sieve in an aqueous solution containing a transition metal precursor, drying and roasting to obtain the catalyst.
7. The method of claim 6, wherein the step of providing the first layer comprises,
The transition metal precursor comprises ammonium metavanadate and soluble nitrate of other transition metals;
In the aqueous solution containing the transition metal precursor, the mass concentration of the transition metal precursor is 1-5wt%;
The solid-to-liquid ratio of the titanium silicon molecular sieve to the aqueous solution containing the transition metal precursor is (10-50): 1g/ml.
8. The method of claim 6, wherein the step of providing the first layer comprises,
The temperature of the impregnation is 30-80 ℃;
the soaking time is 2-6 h;
Stirring in the soaking process;
The drying temperature is 80-120 ℃;
The drying time is 12-20 h;
The roasting temperature is 450-600 ℃;
The roasting time is 2-8 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211617988.7A CN118206436A (en) | 2022-12-15 | 2022-12-15 | Method for preparing cyclopentanone by oxidation of cyclopentane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211617988.7A CN118206436A (en) | 2022-12-15 | 2022-12-15 | Method for preparing cyclopentanone by oxidation of cyclopentane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
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