CN115721901A - Method for decomposing hydrogen peroxide - Google Patents
Method for decomposing hydrogen peroxide Download PDFInfo
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- CN115721901A CN115721901A CN202111016697.8A CN202111016697A CN115721901A CN 115721901 A CN115721901 A CN 115721901A CN 202111016697 A CN202111016697 A CN 202111016697A CN 115721901 A CN115721901 A CN 115721901A
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 147
- 238000000034 method Methods 0.000 title claims abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 92
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 52
- 239000010439 graphite Substances 0.000 claims abstract description 52
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 39
- 239000002086 nanomaterial Substances 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000002904 solvent Substances 0.000 claims abstract description 23
- 239000000243 solution Substances 0.000 claims abstract description 19
- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 150000007529 inorganic bases Chemical class 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 238000004108 freeze drying Methods 0.000 claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000003513 alkali Substances 0.000 claims description 13
- -1 amine compounds Chemical class 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 10
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 10
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 8
- 239000002808 molecular sieve Substances 0.000 claims description 8
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 8
- 239000002585 base Substances 0.000 claims description 7
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 7
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 5
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 claims description 5
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 5
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 5
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 5
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 3
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 150000007530 organic bases Chemical class 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910021392 nanocarbon Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002096 quantum dot Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 230000005476 size effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000011852 carbon nanoparticle Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
Abstract
The present invention relates to a method for decomposing hydrogen peroxide, comprising: s1, electrolyzing a graphite forming body in an aqueous solution containing inorganic base to obtain a liquid mixture; s2, freeze-drying the liquid mixture to obtain an alkaline carbon nano material; and S3, in the presence of an optional solvent, carrying out contact reaction on the alkaline carbon nano material and a solution containing hydrogen peroxide at the temperature of 0-100 ℃ for 1-720min. The method of the invention has good decomposition effect on low-concentration hydrogen peroxide.
Description
Technical Field
The present invention relates to a method for decomposing hydrogen peroxide.
Background
The carbon nano material refers to fine carbon particles with the size of nano-scale (1-100 nm), and similar to common nano materials, the carbon nano material also has special properties such as quantum size effect, small size effect, macroscopic quantum tunneling effect and the like in the aspects of optics, electricity, magnetism and the like. The tiny carbon nano-particles with the size less than 10nm discovered in 2004 when the single-layer carbon nano-tube is purified by an electrophoresis method are named as carbon quantum dots for the first time, and are a novel small-size carbon nano-material. Carbon quantum dots are also referred to as fluorescent carbon quantum dots (CDs) because of their excellent fluorescent properties. In the short few years from the discovery to the utilization of CDs, CDs has become a new star of the carbon nano family. With the research, the materials for synthesizing CDs are more and more abundant, and the synthesis methods used are also infinite. The nature and utilization of various aspects of CDs have also been studied more and more carefully and in the end, with significant progress. In addition to good water solubility, high stability, low toxicity and good biocompatibility, CDs have unique optical and electrical properties compared to organic dyes and conventional semiconductor Quantum Dots (QDs). Therefore, research into the properties and utilization of CDs has received increasing attention.
The hydrogen peroxide is used as a green oxidant and is more and more widely applied to modern chemical industry. In the existing chemical process utilizing hydrogen peroxide, certain residues exist more or less. The residual hydrogen peroxide not only affects the quality of products and increases the separation difficulty of the products, but also has the possibility of explosion and the like, and has large safety risk. There is a high demand for a technique for decomposing and utilizing residual hydrogen peroxide.
Disclosure of Invention
The invention aims to provide a method for decomposing hydrogen peroxide, which has higher decomposition rate of the hydrogen peroxide.
In order to achieve the above object, the present invention provides a method for decomposing hydrogen peroxide, the method comprising:
s1, electrolyzing a graphite forming body in an aqueous solution containing inorganic alkali to obtain a liquid mixture;
s2, freeze-drying the liquid mixture to obtain an alkaline carbon nano material;
and S3, in the presence of an optional solvent, carrying out contact reaction on the alkaline carbon nano material and an aqueous solution of hydrogen peroxide at the temperature of 0-100 ℃ for 1-720min.
Alternatively, in step S1, the content of the inorganic base in the aqueous solution containing the inorganic base is 0.1 to 40% by weight, preferably 0.5 to 25% by weight, and more preferably 1 to 20% by weight.
Optionally, in step S1, the inorganic base is one or more selected from ammonia water, potassium hydroxide, sodium hydroxide, barium hydroxide and calcium hydroxide.
Optionally, in step S1, the electrolytic graphite formed body includes: placing the graphite forming body connected with the positive electrode of the direct current power supply and the conductive forming body connected with the negative electrode of the direct current power supply in an aqueous solution containing inorganic base at the same time, and electrolyzing for 2-10 days under the voltage of 60-120V;
the graphite forming body is a graphite rod or a graphite plate, the diameter of the graphite rod is 2-20mm, the length of the graphite rod is 10-100cm, the length of the graphite plate is 5-100cm, the width of the graphite plate is 1-100cm, and the thickness of the graphite plate is 0.01-10mm; the conductive molded body is an iron rod, an iron plate, a graphite rod, a graphite plate, a copper plate or a copper rod, and preferably the iron rod, the graphite rod or the copper rod;
the distance between the graphite forming body and the conductive forming body is 1-50cm.
Optionally, in step S3, the reaction conditions include: the temperature is 20-100 deg.C, and the time is 1-240min.
Optionally, in step S3, the weight ratio of the alkaline carbon nanomaterial to the amount of the solution containing hydrogen peroxide is (0.1-10): 100, preferably (0.5-2): 100.
alternatively, in step S3, the concentration of the hydrogen peroxide-containing solution is 0.005 to 5 wt%, preferably 0.01 to 2 wt%.
Optionally, step S3 includes: in the presence of organic alkali and optional solvent, the alkali carbon nano material and hydrogen peroxide are contacted and reacted for 1-120min at the temperature of 30-100 ℃;
the weight ratio of the organic alkali to the alkaline carbon nano material is 10: (1-100);
the weight ratio of the alkaline carbon nano material to the solvent is 10: (0-1000);
the organic alkali is selected from one or more of quaternary ammonium base compounds, fatty amine compounds and alcohol amine compounds;
the quaternary ammonium base compound is selected from tetrabutylammonium hydroxide, tetrapropylammonium hydroxide or tetraethylammonium hydroxide, or a combination of two or three of the tetrabutylammonium hydroxide, tetrapropylammonium hydroxide or tetraethylammonium hydroxide;
the aliphatic amine compound is selected from butanediamine, n-butylamine, ethylamine or hexamethylenediamine, or a combination of two or three of the butanediamine, the n-butylamine, the ethylamine or the hexamethylenediamine;
the alcohol amine compound is selected from monoethanolamine, diethanolamine or triethanolamine, or a combination of two or three of the monoethanolamine, diethanolamine and triethanolamine;
the solvent is selected from water and/or alcohol; the alcohol is selected from methanol and/or ethanol.
Optionally, in step S3, when no solvent is present, mixing the basic carbon nanomaterial and the titanium silicalite molecular sieve in a mass ratio of 1: (0.1-2), preferably 1: (0.4-1), and then contacting and reacting with the solution containing the hydrogen peroxide at the temperature of 20-80 ℃ for 5-120min.
Alternatively, the residual amount of hydrogen peroxide in the hydrogen peroxide-containing solution after the completion of the reaction is 0 to 100ppm, preferably 0 to 50ppm, and more preferably 0 to 10ppm.
By adopting the technical scheme, the alkaline carbon nano material is used for decomposing low-concentration hydrogen peroxide, and the decomposition effect is good.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes the embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The present invention provides a method for decomposing hydrogen peroxide, the method comprising:
s1, electrolyzing a graphite forming body in an aqueous solution containing inorganic alkali to obtain a liquid mixture;
s2, freeze-drying the liquid mixture to obtain an alkaline carbon nano material;
and S3, in the presence of an optional solvent, carrying out contact reaction on the alkaline carbon nano material and a solution containing hydrogen peroxide at the temperature of 0-80 ℃ for 1-720min.
The invention applies the alkaline carbon nano material to the decomposition reaction of low-concentration hydrogen peroxide, and the decomposition rate of the hydrogen peroxide is higher.
According to the present invention, the method of the present invention is excellent in the decomposition effect of low-concentration hydrogen peroxide, and the residual amount of hydrogen peroxide in the solution containing hydrogen peroxide after the completion of the reaction is 0 to 100ppm, preferably 0 to 50ppm, and more preferably 0 to 10ppm.
According to the present invention, the content of the inorganic base in the aqueous solution containing the inorganic base in step S1 may vary within a wide range, and may be, for example, 0.1 to 40% by weight, preferably 0.5 to 25% by weight, and more preferably 1 to 20% by weight. The inorganic base can be effectively used in the above concentration range, and a carbon nanomaterial with good reactivity can be prepared.
According to the present invention, in step S1, the electrolytic graphite molded body includes: and (3) putting the graphite forming body connected with the positive electrode of the direct current power supply and the conductive forming body connected with the negative electrode of the direct current power supply into an aqueous solution containing inorganic alkali at the same time, and electrolyzing for 2-10 days under the voltage of 60-120V.
According to the invention, in step S1, the inorganic base is selected from one or more of ammonia, potassium hydroxide, sodium hydroxide, barium hydroxide and calcium hydroxide.
According to the present invention, in step S1, the graphite formed body may be a graphite rod or a graphite plate, and the size of the graphite rod and the graphite plate is not limited, and in one embodiment, the graphite rod has a diameter of 2 to 20mm and a length of 10 to 100cm; the graphite plate has a length of 5-100cm, a width of 1-100cm and a thickness of 0.01-10mm. The conductive molded body is not particularly limited as long as it is a conductive material, and may be, for example, iron, graphite, or copper, and may be, for example, a common rod or plate shape without any requirement for the shape. In one embodiment, the electrically conductive shaped body is an iron rod, an iron plate, a graphite rod, a graphite plate, a copper plate or a copper rod, preferably an iron rod, a graphite rod or a copper rod, more preferably a graphite rod matching the graphite shaped body. During electrolysis, a certain distance can be maintained between the graphite shaped body and the electrically conductive shaped body, which can vary within a relatively large range, for example from 1 to 50cm, preferably from 1 to 20cm.
According to the present invention, in step S3, the reaction conditions may preferably include: the temperature is 20-100 deg.C, and the time is 1-240min. The method is favorable for efficient decomposition of the hydrogen peroxide under the mild reaction condition, and has low requirements on equipment and devices and the like. The reaction can be carried out in an open container, for example, a flask in a laboratory, or in a closed container, for example, a closed stainless steel reaction kettle, and the reaction can be carried out under stirring in order to allow the alkaline carbon nanomaterial and the hydrogen peroxide to be sufficiently reacted in contact with each other.
According to the invention, the weight ratio of the amount of alkaline carbon nanomaterial to the hydrogen peroxide-containing solution used in step S3 may vary within wide limits, and may be, for example, (0.1-10): 100, preferably (0.5-2): 100. within the above range, the alkaline carbon nanomaterial has a better reaction effect with hydrogen peroxide, and hydrogen peroxide can be removed to the maximum extent.
According to the invention, step S3 comprises: in the presence of organic alkali and optional solvent, the alkali carbon nano material and hydrogen peroxide are contacted and reacted for 1-120min at 30-100 ℃. The weight ratio of the organic base to the alkaline carbon nanomaterial may vary within a wide range, and may be, for example, 10: (1-100). The weight ratio of the amount of basic carbon nanomaterial and solvent may also vary over a wide range, and may be, for example, 10: (0-1000).
In a preferred embodiment, in the presence of organic base and solvent, the alkaline carbon nano material is contacted with hydrogen peroxide at 30-60 ℃ for reaction for 10-60min, and the weight ratio of the organic base to the alkaline carbon nano material is 10: (10-50). The weight ratio of the alkaline carbon nano material to the solvent is 10: (0-100). The kind of the solvent is not particularly limited in the present invention as long as it does not react with the basic carbon nanomaterial and the hydrogen peroxide, and may be, for example, water and/or alcohol, and preferably one or more selected from water, methanol, and ethanol.
According to the present invention, the organic base is well known to those skilled in the art, and may be selected from one or more of quaternary ammonium base compounds, fatty amine compounds and alcohol amine compounds, for example.
In one embodiment of the present invention, the quaternary ammonium base compound may have a general molecular formula of (R) 1 ) 4 NOH wherein R 1 May be selected from C 1 -C 4 Straight chain alkyl of (2) and C 3 -C 4 At least one of branched alkyl groups of (a). Preferably, the quaternary ammonium base compound is selected from tetrabutylammonium hydroxide, tetrapropylammonium hydroxide or tetraethylammonium hydroxide, or a combination of two or three thereof.
The molecular general formula of the aliphatic amine compound can be R 2 (NH 2 ) n Wherein R is 2 Can be C 1 -C 6 Straight chain alkyl of (2) and C 3 -C 6 At least one of branched alkyl groups of (a). Preferably, the aliphatic amine compound is selected from butanediamine, n-butylamine, ethylamine or hexamethylenediamine, or a combination of two or three thereof.
The molecular general formula of the alcohol amine compound can be (HOR) 3 ) m NH (3-m) Wherein R is 3 Can be C 1 -C 4 M is an integer of 1, 2 or 3. Preferably, the alkanolamine compound is selected from monoethanolamine, diethanolamine or triethanolamine, or a combination of two or three thereof.
In another embodiment of the present invention, in step S3, when no solvent is present, the concentration of the aqueous solution containing hydrogen peroxide is 0.005 to 5% by weight, preferably 0.01 to 2% by weight; in another embodiment, the concentration of the hydrogen peroxide-containing solution after solvent dilution is 0.005-2 wt.%, preferably 0.05-1 wt.%, when other non-aqueous solvents are present. The method of the invention is particularly suitable for the decomposition process of hydrogen peroxide at low concentrations.
In an embodiment of the present invention, step S3 may further include: when no solvent exists, mixing the alkaline carbon nano material and the titanium silicalite molecular sieve according to the mass ratio of 1: (0.1-2), preferably 1: (0.4-1), and then is contacted with a solution containing hydrogen peroxide at the temperature of 20-80 ℃ for reaction for 5-120min. The hydrogen peroxide can be decomposed more thoroughly under the conditions, and the residual amount of the hydrogen peroxide in the solution containing the hydrogen peroxide after the reaction is finished can be less than 10ppm, so that the treated hydrogen peroxide solution is safer. Wherein, the titanium silicalite molecular sieve can be one or more selected from titanium silicalite molecular sieves with MFI structure, MOR structure and BEA structure, and is preferably a titanium silicalite molecular sieve with MFI structure; the titanium silicalite molecular sieve may have a silicon to titanium molar ratio of from 15 to 100, preferably from 20 to 50.
Freeze-drying is routinely employed by those skilled in the art in accordance with the present invention, and conditions for freeze-drying may include: the temperature is-80 ℃ to 0 ℃, the time is 1 to 72 hours, and the vacuum degree is 5 to 10000Pa; preferably, the temperature is-60 ℃ to-15 ℃, the time is 6-36 hours, and the vacuum degree is 100-2000Pa. The alkaline carbon nano material obtained by freeze drying has a porous structure and stable physicochemical property, and has good reactivity when reacting with hydrogen peroxide.
The invention is further illustrated by the following examples, but is not to be construed as being limited thereto.
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The residual amount of hydrogen peroxide in the solution containing hydrogen peroxide after the reaction was analyzed by a chemical titration analysis method.
Example 1
S1, adding 5000mL of sodium hydroxide aqueous solution with the concentration of 5 wt% into a beaker to serve as electrolyte, placing an anode graphite rod (with the diameter of 8mm and the length of 50 cm) and a cathode graphite rod (with the diameter of 8mm and the length of 50 cm) in the beaker, keeping the distance between the anode graphite rod and the cathode rod at 5cm, connecting the anode graphite rod with the positive pole of a direct current power supply, connecting the cathode rod with the negative pole of the direct current power supply, and applying 65V voltage to electrolyze for 3 days to obtain a liquid mixture;
s2, freeze-drying the liquid mixture at-30 ℃ and a vacuum degree of 100Pa for 24 hours to obtain an alkaline nano-carbon material;
s3, mixing 28g of methanol, 0.5g of n-butylamine, 0.5g of basic nanocarbon material and 30g of aqueous solution (1 wt%) of hydrogen peroxide, putting the mixture into a stainless steel reaction kettle, sealing the mixture until the concentration of the hydrogen peroxide is 0.5 wt%, stirring the mixture at the temperature of 60 ℃ for reaction for 1 hour, taking the mixture out, and analyzing the residual amount of the hydrogen peroxide after the reaction.
Example 2
Hydrogen peroxide was decomposed in the same manner as in example 1, except that the electrolyte in step S1 was 5000mL of an aqueous solution of sodium hydroxide having a concentration of 0.4% by weight.
Example 3
The hydrogen peroxide was decomposed in the same manner as in example 1, except that the reaction temperature was 10 ℃ and the reaction time was 5 hours in step S3.
Example 4
Hydrogen peroxide was decomposed in the same manner as in example 1, except that in step S3, 0.5g of the basic nanocarbon material and 17g of an aqueous solution (1 wt%) of hydrogen peroxide were placed in a stainless steel reaction vessel.
Example 5
Hydrogen peroxide was decomposed in the same manner as in example 1, except that n-butylamine, an organic base, was not added in step S3.
Example 6
The hydrogen peroxide was decomposed in the same manner as in example 1, except that methanol as a solvent was not added in step S3.
Example 7
Hydrogen peroxide was decomposed in the same manner as in example 1, except that n-butylamine, an organic base, and methanol, a solvent, were not added in step S3.
Example 8
Hydrogen peroxide was decomposed in the same manner as in example 1, except that in step S3, 7.8g of methanol, 0.5g of n-butylamine, 0.5g of an alkaline nanocarbon material and 30g of an aqueous solution (4% by weight) of hydrogen peroxide were mixed and placed in a stainless steel reaction vessel, and the concentration of hydrogen peroxide in the mixture was 3% by weight.
Example 9
Hydrogen peroxide was decomposed in the same manner as in example 1, except that in step S3, the organic base n-butylamine and the solvent methanol were not added, and the basic carbon nanomaterial and the titanium silicalite molecular sieve having an MFI structure were mixed in the following ratio of 1:0.5, and then the mixture is contacted with a solution containing hydrogen peroxide for reaction.
Comparative example 1
0.5g of manganese dioxide and 30g of an aqueous solution (1 wt%) of hydrogen peroxide were mixed and put into a stainless steel reaction vessel, and after sealing, the reaction was stirred at 60 ℃ for 1 hour, and after taking out, the residual amount of hydrogen peroxide after the reaction was analyzed.
TABLE 1
| Sample source | Residual amount of hydrogen peroxide, ppm |
| Example 1 | 15 |
| Example 2 | 23 |
| Example 3 | 35 |
| Example 4 | 28 |
| Example 5 | 67 |
| Example 6 | 72 |
| Example 7 | 91 |
| Example 8 | 62 |
| Example 9 | 8 |
| Comparative example 1 | 504 |
From the results of the examples and comparative examples, it is understood that the method of the present invention can effectively decompose hydrogen peroxide at a low concentration.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. A method of decomposing hydrogen peroxide, the method comprising:
s1, electrolyzing a graphite forming body in an aqueous solution containing inorganic base to obtain a liquid mixture;
s2, freeze-drying the liquid mixture to obtain an alkaline carbon nano material;
and S3, in the presence of an optional solvent, carrying out contact reaction on the alkaline carbon nano material and a solution containing hydrogen peroxide at the temperature of 0-100 ℃ for 1-720min.
2. The process according to claim 1, wherein in step S1, the content of the inorganic base in the aqueous solution containing the inorganic base is 0.1 to 40 wt%, preferably 0.5 to 25 wt%, and more preferably 1 to 20 wt%.
3. The method according to claim 1 or 2, wherein in step S1, the inorganic base is selected from one or more of ammonia, potassium hydroxide, sodium hydroxide, barium hydroxide and calcium hydroxide.
4. The method according to claim 1, wherein in step S1, the electrolytic graphite formed body comprises: placing the graphite forming body connected with the positive electrode of the direct current power supply and the conductive forming body connected with the negative electrode of the direct current power supply in an aqueous solution containing inorganic base at the same time, and electrolyzing for 2-10 days under the voltage of 60-120V;
the graphite forming body is a graphite rod or a graphite plate, the diameter of the graphite rod is 2-20mm, the length of the graphite rod is 10-100cm, the length of the graphite plate is 5-100cm, the width of the graphite plate is 1-100cm, and the thickness of the graphite plate is 0.01-10mm; the conductive molded body is an iron rod, an iron plate, a graphite rod, a graphite plate, a copper plate or a copper rod, and preferably the iron rod, the graphite rod or the copper rod;
the distance between the graphite forming body and the conductive forming body is 1-50cm.
5. The method of claim 1, wherein in step S3, the conditions of the reaction comprise: the temperature is 20-100 deg.C, and the time is 1-240min.
6. The method according to claim 1, wherein in step S3, the weight ratio of the alkaline carbon nanomaterial to the amount of the solution containing hydrogen peroxide is (0.1-10): 100, preferably (0.5-2): 100.
7. the process according to claim 6, wherein in step S3, the concentration of the solution containing hydrogen peroxide is 0.005-5 wt.%, preferably 0.01-2 wt.%.
8. The method of claim 1, wherein step S3 comprises: in the presence of organic alkali and optional solvent, the alkali carbon nano material and hydrogen peroxide are contacted and reacted for 1-120min at the temperature of 30-100 ℃;
the weight ratio of the organic alkali to the alkaline carbon nano material is 10: (1-100);
the weight ratio of the alkaline carbon nano material to the solvent is 10: (0-1000);
the organic alkali is selected from one or more of quaternary ammonium base compounds, fatty amine compounds and alcohol amine compounds;
the quaternary ammonium base compound is selected from tetrabutylammonium hydroxide, tetrapropylammonium hydroxide or tetraethylammonium hydroxide, or a combination of two or three of the tetrabutylammonium hydroxide, tetrapropylammonium hydroxide or tetraethylammonium hydroxide;
the aliphatic amine compound is selected from butanediamine, n-butylamine, ethylamine or hexamethylenediamine, or a combination of two or three of the butanediamine, the n-butylamine and the ethylamine;
the alcohol amine compound is selected from monoethanolamine, diethanolamine or triethanolamine, or a combination of two or three of the monoethanolamine, diethanolamine and triethanolamine;
the solvent is selected from water and/or alcohol; the alcohol is selected from methanol and/or ethanol.
9. The method of claim 1, wherein in step S3, when no solvent is present, the basic carbon nanomaterial and the titanium silicalite molecular sieve are mixed in a mass ratio of 1: (0.1-2), preferably 1: (0.4-1), and then contacting and reacting with the solution containing the hydrogen peroxide at the temperature of 20-80 ℃ for 5-120min.
10. The process according to claim 1, wherein the residual amount of hydrogen peroxide in the solution containing hydrogen peroxide after the completion of the reaction is 0 to 100ppm, preferably 0 to 50ppm, more preferably 0 to 10ppm.
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| US20090093582A1 (en) * | 2007-10-09 | 2009-04-09 | Headwaters Technology Innovation, Llc | Functionalization of carbon nanoshperes by severe oxidative treatment |
| CN111068732A (en) * | 2019-12-20 | 2020-04-28 | 江苏永葆环保科技有限公司 | Hydrogen peroxide decomposition catalyst and application thereof in semiconductor waste acid treatment |
| CN111760565A (en) * | 2019-04-01 | 2020-10-13 | 中国石油化工股份有限公司 | Modified nano carbon-based material and preparation method thereof and catalytic oxidation method of cyclic hydrocarbon |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20090093582A1 (en) * | 2007-10-09 | 2009-04-09 | Headwaters Technology Innovation, Llc | Functionalization of carbon nanoshperes by severe oxidative treatment |
| CN111760565A (en) * | 2019-04-01 | 2020-10-13 | 中国石油化工股份有限公司 | Modified nano carbon-based material and preparation method thereof and catalytic oxidation method of cyclic hydrocarbon |
| CN111068732A (en) * | 2019-12-20 | 2020-04-28 | 江苏永葆环保科技有限公司 | Hydrogen peroxide decomposition catalyst and application thereof in semiconductor waste acid treatment |
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