CN111747847B - Method for alkane selective catalytic oxidation reaction - Google Patents

Method for alkane selective catalytic oxidation reaction Download PDF

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CN111747847B
CN111747847B CN202010604199.4A CN202010604199A CN111747847B CN 111747847 B CN111747847 B CN 111747847B CN 202010604199 A CN202010604199 A CN 202010604199A CN 111747847 B CN111747847 B CN 111747847B
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alkane
copper salt
methane
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CN111747847A (en
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李苏华
刘路遥
陈晓妍
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Sun Yat Sen University
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Abstract

The invention discloses a method for high-efficiency selective reaction of catalytic oxidation of alkane. Alkane is taken as a raw material, and reacts in a trifluoroacetic acid and/or trifluoroacetic anhydride system and a copper salt-metal salt as a catalytic system in the presence of an oxidant to generate selective catalytic oxidation reaction; wherein the metal salt is one or more of lithium salt, sodium salt, potassium salt, cesium salt, calcium salt or magnesium salt. The metal salt is used as the catalyst auxiliary agent and is matched with the copper salt for use, so that the reaction activity of the catalyst in catalytic oxidation of alkane is remarkably improved, the high yield of the product is ensured, the using amount of the catalyst is remarkably reduced, and the catalytic efficiency of the catalyst is improved. Using methane as an example, the above procedure produces methane trifluoroacetate in a maximum yield of about 72% and a selectivity of about 92%. The reaction process has relatively mild conditions, the reaction can be carried out at 90 ℃, and the obtained methyl trifluoroacetate can be subjected to various conversions according to literature methods, such as hydrolysis into trifluoroacetic acid and methanol.

Description

Method for alkane selective catalytic oxidation reaction
Technical Field
The invention relates to the technical field of methane catalytic oxidation, in particular to a method for high-efficiency selective reaction of catalytic oxidation of alkane.
Background
Methane, which is the most abundant fuel on earth as a main component of natural gas and biogas, is increasingly regarded for chemical conversion due to the sustainable development of human society. One particular direction in these conversion processes is the selective oxidation of methane to methanol, one of the most demanding industrial chemicals, which is widely used in many fields. However, due to the high symmetry of the structure, with four identical C-H bonds, no dipole moment and low polarizability, methane activation becomes quite difficult. Another challenge in this field is peroxidation, since MeOH is more reactive than methane under most methane activation conditions, and methanol is more easily over-oxidized to formaldehyde, formic acid, or CO during the reaction2. To avoid the problem of over-oxidation, one of the most common strategies is the in situ generation of protected methanol, such as methyl hydrogen sulfate or methyl trifluoroacetate, which inhibits peroxidation.
At present, the efficiency of the reaction for selectively preparing methanol or methanol derivatives from methane is generally low, and the by-products of the reaction are too many, so that the selectivity of the target product is low, and the yield is low. Currently, there are many studies on the preparation of methyl trifluoroacetate by catalytic oxidation of methane, for example, patent CN200910237793.8 provides a copper-containing catalyst for catalytic oxidation of methane under low temperature conditions; CN200910241378X investigated the effect of reaction solvent on catalytic oxidation of methane; patents US5585515, WO2004069784, US2007149832 and WO2007073533 report methane catalytic oxidation reactions in trifluoroacetic acid systems; however, in the above conventional method, the conversion rate of methane is low, and the difficulty in practical application is large. To solve this problem, Guochean Yin et al 2000 (appl. organometal. chem.2000,14, 438-2/K2S2O8The catalytic system is effective in converting methane to methyl trifluoroacetate. Although the conversion of methane and the yield of the product are higher in this scheme, the catalyst is used in a larger amountThat is, the catalytic reaction efficiency of the catalyst has a large promotion space, and therefore, it is necessary to solve the problem to improve the industrial feasibility.
Disclosure of Invention
The invention aims to provide application of a metal salt as a catalyst promoter in alkane selective catalytic oxidation reaction. The metal salt is used as a catalyst auxiliary agent and matched with copper salt for use, so that the catalyst in alkane, especially C, is remarkably improved1～16The activity of alkane catalytic oxidation reaction obviously reduces the dosage of the catalyst and improves the catalytic efficiency while ensuring high yield of the product.
Another object of the present invention is to provide a method for the selective catalytic oxidation of alkanes with high efficiency.
The invention also aims to provide a method for preparing methyl trifluoroacetate by efficiently catalyzing and oxidizing methane.
The above object of the present invention is achieved by the following scheme:
the application of metal salt as catalyst auxiliary agent in alkane selective catalytic oxidation reaction, in trifluoroacetic acid and/or trifluoroacetic anhydride system, copper salt as catalyst, metal salt as auxiliary agent, under the condition of oxidant existence, selective catalytic oxidation alkane reaction, preparing specific product; wherein the metal salt is one or more of lithium salt, sodium salt, potassium salt, cesium salt, calcium salt or magnesium salt.
In the reaction process, firstly, copper salt catalyzes persulfate to react to generate persulfate anions and persulfate radicals, wherein the persulfate radicals grab hydrogen on alkane to obtain alkyl radicals, and meanwhile, copper oxidizes the alkyl radicals to form alkyl cations; then reacting the alkyl positive ions with trifluoroacetic acid to obtain a product of selective catalytic oxidation; the addition of the metal salt greatly promotes the ionization of trifluoroacetic acid and increases the concentration of negative ions of the trifluoroacetic acid, thereby improving the reaction rate of the alkyl positive ions and the negative ions of the trifluoroacetic acid and greatly improving the reaction efficiency.
Preferably, the metal salt is LiF, NaF, NaCl, NaHF2、NaFPO3、KF、KCl、KHF2、K2CO3、K2SO4、K3PO4、KOTFA、CsF、Cs2CO3One or more of CsOAc or CaO.
More preferably, the metal salt is KF or NaF.
Preferably, the copper salt is a monovalent copper salt or a divalent copper salt.
Preferably, the copper salt is CuCl, CuBr, CuI, CuCl2，CuOAc，Cu(OAc)2Or Cu (OTf)2。
Preferably, the oxidizing agent is a persulfate; more preferably, the oxidizing agent is potassium persulfate or sodium persulfate.
Preferably, the alkane is unsubstituted C1～16Linear, branched or cyclic alkanes; more preferably, is C1～10Linear, branched or cyclic alkanes; most preferably, methane.
The invention also discloses a method for high-efficiency selective catalytic oxidation of alkane, which takes alkane as a raw material, takes copper salt-metal salt as a catalytic system in a trifluoroacetic acid and/or trifluoroacetic anhydride system, and reacts in the presence of an oxidant to perform selective catalytic oxidation; wherein the metal salt is one or more of lithium salt, sodium salt, potassium salt, cesium salt, calcium salt or magnesium salt.
Preferably, the metal salt is LiF, NaF, NaCl, NaHF2、NaFPO3、KF、KCl、KHF2、K2CO3、K2SO4、K3PO4、KOTFA、CsF、Cs2CO3One or more of CsOAc or CaO.
More preferably, the metal salt is KF or NaF.
Preferably, the copper salt is a monovalent copper salt or a divalent copper salt.
Preferably, the copper salt is CuCl, CuBr, CuI, CuCl2，CuOAc，Cu(OAc)2Or Cu (OTf)2。
Preferably, the oxidizing agent is a persulfate; more preferably, the oxidizing agent is potassium persulfate or sodium persulfate.
Preferably, the alkane is unsubstituted C1～16Linear, branched or cyclic alkanes; more preferably, is C1～10Linear, branched or cyclic alkanes; most preferably, methane.
The invention also discloses a method for preparing methyl trifluoroacetate by efficiently catalyzing and oxidizing methane, which comprises the steps of taking methane as a raw material, taking copper salt-metal salt as a catalytic system in a trifluoroacetic acid and/or trifluoroacetic anhydride system, and reacting in the presence of an oxidant to prepare methyl trifluoroacetate; wherein the metal salt is one or more of lithium salt, sodium salt, potassium salt, cesium salt, calcium salt or magnesium salt.
Preferably, the metal salt is LiF, NaF, NaCl, NaHF2、NaFPO3、KF、KCl、KHF2、K2CO3、K2SO4、K3PO4、KOTFA、CsF、Cs2CO3One or more of CsOAc or CaO.
More preferably, the metal salt is KF or NaF.
Preferably, the copper salt is a monovalent copper salt or a divalent copper salt.
Preferably, the copper salt is CuCl, CuBr, CuI, CuCl2，CuOAc，Cu(OAc)2Or Cu (OTf)2。
Preferably, the oxidizing agent is a persulfate; more preferably, the oxidizing agent is potassium persulfate or sodium persulfate.
Preferably, the reaction pressure is 30 to 50 bar.
Preferably, the reaction molar ratio of the oxidant/copper salt/metal salt is 10: 0.001-0.5: 1-3.
Preferably, the reaction temperature is 60-120 ℃, and the reaction time is 5-30 h.
Compared with the prior art, the invention has the following beneficial effects:
(1) the metal salt is used as the catalyst auxiliary agent and is matched with the copper salt for use, so that the reaction activity of the catalyst in catalytic oxidation of alkane is remarkably improved, the high yield of the product is ensured, the using amount of the catalyst is remarkably reduced, and the catalytic efficiency of the catalyst is improved;
(2) the selective oxidation reaction of alkane is realized by taking copper salt and metal salt auxiliary agent as a catalytic system, only one-step reaction is needed, the reaction process conditions are relatively mild, the reaction raw materials are cheap and easy to obtain, and the cost is low; the reaction efficiency is high, and the selectivity of the product is high;
(3) in the method for preparing the methyl trifluoroacetate by catalytic oxidation of methane, the highest yield of the methyl trifluoroacetate is about 72 percent, and the selectivity is about 92 percent. The reaction process has relatively mild conditions, and the preparation can be carried out at 90 ℃.
Detailed Description
The present invention is further described in detail below with reference to specific examples, which are provided for illustration only and are not intended to limit the scope of the present invention. The test methods used in the following examples are all conventional methods unless otherwise specified; the materials, reagents and the like used are, unless otherwise specified, commercially available reagents and materials.
In the following examples, the yield of the product was calculated as:
methyl trifluoroacetate yield-methyl trifluoroacetate yield/amount of potassium persulfate used-100%. Selectivity-100% of the amount of species of methyl trifluoroacetate in the product compared to the amount of species of all methane oxidation products.
Example 1
In this embodiment, taking methane as an example, a method for preparing methyl trifluoroacetate by catalytic oxidation of methane is explored, and the specific process is as follows: the methyl trifluoroacetate is prepared by taking methane as a raw material, taking copper salt-metal salt as a catalytic system in a trifluoroacetic acid and/or trifluoroacetic anhydride system, and reacting in the presence of an oxidant potassium persulfate.
Figure BDA0002560333830000041
In the above reaction process, the influence of each reaction condition on the reaction was investigated:
1. investigating the reactivity of different metal salts
The method takes methane as a raw material, cuprous chloride and different metal salt assistants as catalytic systems to carry out reaction, and the specific reaction formula is as follows:
Figure BDA0002560333830000042
the reaction pressure of methane is 30bar, the catalyst is CuCl (0.5M in conc. HCl), the addition amount in the reaction is 10ul, 0.001mmol, K2S2O8The amount is 10mmol, but not particularly limited, the amount of the metal salt is 3mmol, the amount of TFA is 15mL, the amount of TFAA is 2.5mL, the reaction temperature is 90 ℃ and the reaction time is 20 h.
The yields of the different kinds of metal salts used in the reaction and the products obtained are shown in table 1.
TABLE 1 yield results for various metal salt promoters and reaction products thereof
Figure BDA0002560333830000043
Figure BDA0002560333830000051
In table 1:ayield as CH2Br2Calibrating for an internal standard;bK3PO4 1mmol；cadding 10ul conc. HCl without CuCl;dCs2CO3 1.5mmol.；eCuCl and metal salt are not added;fCuCl (0.5M in conc. HCl) was freshly prepared and 10ul was added to the reaction.
As is clear from the results shown in Table 1, the influence of the kind of the metal salt assistant on the reaction is significant, and when the metal salt is CaF2And MgSO4When the metal salt is NaCl, KCl or Na, the yield of the reaction is low2FPO3、K2CO3、K2SO4、KOTFA、K3PO4、CsF、Cs2CO3CsOAc, CaO and LiF, and the yield of reaction products is moderate; when the metal salts are NaF and KF, the yield of the reaction product is high.
2. Investigating the influence of the amount of KF on the reaction
Methane is used as a raw material, cuprous chloride and potassium fluoride are used as a catalytic system, KF with different amounts reacts, and the specific reaction formula is as follows:
Figure BDA0002560333830000052
the reaction pressure of methane is 30bar, the catalyst is CuCl (0.5M in conc. HCl), the addition amount in the reaction is 10ul, 0.001mmol, K2S2O8The dosage is 10mmol, the addition amount of TFA is 15mL, the addition amount of TFAA is 2.5mL, the reaction temperature is 90 ℃, and the reaction time is 20 h.
The amount of KF added and the yield of the product obtained by the reaction are shown in Table 2.
TABLE 2 yield results for varying amounts of KF and its reaction products
entry KF/mmol Yield of CF3COOCH3/mmol Yield of Selectivity is
1 2 3.92 39％ 76％
2 3 4.62 46％ 84％
3 4 4.10 41％ 81％
From the results shown in Table 2, the reaction was not greatly affected by the amount of KF added, but the reaction efficiency was the highest when the amount of KF added was 3 mmol.
3. Exploring CH4Influence of pressure on the reaction
Methane is used as a raw material, cuprous chloride and potassium fluoride are used as catalytic systems, and different CH4The reaction is carried out under pressure, and the specific reaction formula is as follows:
Figure BDA0002560333830000061
the catalyst is CuCl (0.5M in conc. HCl), which is newly prepared, and the addition amount in the reaction is 10ul, 0.001mmol and K2S2O8The dosage is 10mmol, the KF addition is 3mmol, the TFA addition is 15mL, the TFAA addition is 2.5mL, the reaction temperature is 90 ℃, and the reaction time is 20 h.
The amount of methane used and the yield of the product obtained by the reaction are shown in Table 3.
TABLE 3 different CHs4Pressure and yield results of reaction products thereof
Entry P(CH4)/bar Yield of CF3COOCH3/mmol Yield of Selectivity is
1 30 4.62 46％ 84％
2 40 5.00 50％ 82％
3 50 5.23 52％ 78％
From the results in Table 3, CH4The pressure of (A) has a certain influence on the reaction, and only 30-50 bar CH is explored in consideration of feasibility of actual operation conditions4The influence on the reaction is that the reaction is influenced,viewed in terms of existing data, in CH4The efficiency of the reaction is highest at a pressure of 50 bar.
4. The influence of the input amount of CuCl on the reaction is explored
The method is characterized in that methane is used as a raw material, cuprous chloride and potassium fluoride are used as a catalytic system, and the reaction is carried out under different amounts of CuCl, and the specific reaction formula is as follows:
Figure BDA0002560333830000062
the reaction pressure of methane is 50bar, and the catalyst is CuCl or K when not specially limited2S2O8The dosage is 10mmol, the KF addition is 3mmol, the TFA addition is 15mL, the TFAA addition is 2.5mL, the reaction temperature is 90 ℃, and the reaction time is 20 h.
The amounts of CuCl added and the yields of the products obtained by the reaction are shown in Table 4.
TABLE 4 yield results for various amounts of CuCl and reaction products thereof
Entry n(CuCl)/mmol Yield of CF3COOCH3/mmola Yield of Selectivity is
1 0.001g 5.23 52％ 78％
2 0.0025h 6.47 65％ 84％
3 0.005i 7.12 71％ 88％
4 0.05 7.15 72％ 92％
5b 0.005 7.00 70％ 88％
6c 0.005 0.38 4％ 29％
7d 0.005 0.28 3％ 22％
8 0 0.96 10％ 22％
9e 0.005 6.95 70％ 92％
10f 0.05 1.40 14％ 76％
In the context of Table 4, the following examples are,ayield as CH2Br2Calibrating for an internal standard;b Cu(OAc)2(0.25M in TFA) for the new preparation, 20ul was added during the reaction;cKF is not added;d 0.005mmol Cu(OAc)2KF is not added;ethe autoclave was replaced three times with methane (oxygen removed);fKF is not added;gCuCl (0.1M in conc. HCl) is a new configuration, 10ul is added in the reaction;hCuCl (0.25M in conc. HCl) is newly prepared, and 10ul is added in the reaction;iCuCl (0.5M in conc. HCl) was added to the reaction in 10ul as a fresh configuration.
The highest yield reported in appl.organometal.chem.2000,14,438-442, calculated by calculating the amount before and after the methane reaction by GC, was 96%. However, according to the ideal gas equation, under such conditions, the amount of the substance of methane gas at 5 atm, from which the solvent and the added reagent were removed in the 25mL reaction vessel, was about 3mmol, which was stillIrrespective of the dissolution of methane in the solvent. At atmospheric pressure, methane has a certain solubility in the solvent, and the solubility increases under pressure, resulting in a true amount of methane higher than 3 mmol. Therefore, there is a large error in the calculation of the yield of methyl trifluoroacetate (1.64mmol) by measuring the amount before and after the methane reaction by GC to be 96%. Because it is difficult to calculate the amount of methane accurately, the present invention selects the amount of potassium persulfate as the basis for accuracy, and 1mmol of potassium persulfate theoretically produces at most 1mmol of methyl trifluoroacetate by mechanism. Thus, according to this calculation method, the highest catalytic efficiency condition of the literature is to use 0.054mmmol Cu (OAc)25mmol of potassium persulfate was reacted with 20 atmospheres of methane for 30 hours in 81% yield instead of 96%.
Analysis according to the results in Table 4 revealed that the amount of CuCl increased from 0.001mmol to 0.05mmol (runs 1-4), the amount of product increased all the time, reaching a maximum already at 0.005mmol, 7.12 mmol; further increasing the catalyst loading to 0.05mmol was similar to the 0.005mmol results, demonstrating that the system can achieve optimal catalytic efficiency already at a catalyst loading of 0.005mmol CuCl. Further, when the amount of the catalyst used was 0.005mmol, Cu (OAc)2The catalytic efficiency of (7 mmol of the product) was slightly lower than that of CuCl (7.12mmol of the product), and in the case of 0.005mmol of CuCl, the amount of the product was only 0.38mmol without addition of KF. It can be seen that when KF is added, the amount of catalyst can be reduced to one tenth of that without KF, and the yield of product can be ensured not to be reduced. Namely, after KF is added, the catalytic action of the copper salt catalyst can be obviously improved, the reaction efficiency is improved, and the dosage of the catalyst is greatly reduced while high yield is ensured.
5. Investigating the influence of time on the reaction
The method takes methane as a raw material, cuprous chloride and potassium fluoride as a catalytic system, and the reaction is carried out for different times, wherein the specific reaction formula is as follows:
Figure BDA0002560333830000081
the reaction pressure of the methane is 50bar, the catalyst is CuCl and K2S2O8The amount was 10mmol, KF addition 3mmol, TFA addition 15mL, TFAA addition 2.5mL, and reaction temperature 90 ℃.
The reaction time and the yield of the product obtained by the reaction are shown in Table 5.
TABLE 5 reaction times in various amounts and the results of the yields of the reaction products
Entry X/h n(CF3COOCH3)/mmol Yield of Selectivity is
1 10 5.55 56％ 86％
2 20 7.12 71％ 88％
3 30 7.21 72％ 89％
According to analysis, the yield is increased along with the increase of the reaction time in the reaction time of 10-30 h, but the reaction efficiency is basically highest (7.12mmol) at the reaction time of 20 h.
Example 2
The best experimental conditions explored in example 1 were extended to the oxidation of other alkanes as follows:
Figure BDA0002560333830000091
the method is also suitable for catalytic oxidation reaction of other alkanes, and selective oxidation products can be prepared.
It should be finally noted that the above examples are only intended to illustrate the technical solutions of the present invention, and not to limit the scope of the present invention, and that other variations and modifications based on the above description and thought may be made by those skilled in the art, and that all embodiments need not be exhaustive. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.

Claims (7)

1. The application of metal salt as catalyst auxiliary agent in alkane selective catalytic oxidation reaction is characterized in that copper salt is used as catalyst and metal salt is used as auxiliary agent in trifluoroacetic acid and/or trifluoroacetic anhydride system, alkane selective catalytic oxidation reaction is carried out under the condition of oxidant existence, and specific product is prepared; wherein the metal salt is LiF, NaF, NaCl, or NaHF2、NaFPO3、KF、KCl、KHF2、K2CO3、K2SO4、K3PO4、KOTFA、CsF、Cs2CO3One or more of CsOAc or CaO.
2. The use according to claim 1, wherein the copper salt is a monovalent copper salt or a divalent copper salt; the oxidant is persulfate.
3. Use according to claim 2, wherein the alkane is unsubstituted C1～16Straight, branched or cyclic alkanes.
4. A method for high-efficiency selective reaction of catalytic oxidation alkane is characterized in that alkane is used as a raw material, copper salt-metal salt is used as a catalytic system in a trifluoroacetic acid and/or trifluoroacetic anhydride system, and the reaction is carried out in the presence of an oxidant to carry out selective catalytic oxidation reaction; wherein the metal salt is LiF, NaF, NaCl, or NaHF2、NaFPO3、KF、KCl、KHF2、K2CO3、K2SO4、K3PO4、KOTFA、CsF、Cs2CO3One or more of CsOAc or CaO.
5. The method of claim 4, wherein the copper salt is a monovalent copper salt or a divalent copper salt; the oxidant is persulfate; the alkane being unsubstituted C1～16Straight, branched or cyclic alkanes.
6. A method for preparing methyl trifluoroacetate by efficiently catalyzing and oxidizing methane is characterized in that methane is used as a raw material, copper salt-metal salt is used as a catalytic system in a trifluoroacetic acid and/or trifluoroacetic anhydride system, and the reaction is carried out in the presence of an oxidant to prepare the methyl trifluoroacetate; wherein the metal salt is LiF, NaF, NaCl, or NaHF2、NaFPO3、KF、KCl、KHF2、K2CO3、K2SO4、K3PO4、KOTFA、CsF、Cs2CO3One or more of CsOAc or CaO.
7. The method for preparing methyl trifluoroacetate from methane through high efficiency catalytic oxidation according to claim 6, wherein the copper salt is a monovalent copper salt or a divalent copper salt; the oxidant is persulfate.
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