WO2020098162A1 - 催化氧化糠醛制备马来酸的催化剂及其制备方法和应用 - Google Patents

催化氧化糠醛制备马来酸的催化剂及其制备方法和应用 Download PDF

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WO2020098162A1
WO2020098162A1 PCT/CN2019/074023 CN2019074023W WO2020098162A1 WO 2020098162 A1 WO2020098162 A1 WO 2020098162A1 CN 2019074023 W CN2019074023 W CN 2019074023W WO 2020098162 A1 WO2020098162 A1 WO 2020098162A1
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furfural
maleic acid
catalyst
catalytic oxidation
preparation
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French (fr)
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李文志
杨涛
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合肥能源研究院
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • B01J23/04—Alkali metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/08—Halides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/08—Halides
    • B01J27/10—Chlorides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B01J27/25—Nitrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/04—Mixing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/084—Decomposition of carbon-containing compounds into carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/285—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with peroxy-compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/31—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
    • C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
    • C07C57/13—Dicarboxylic acids
    • C07C57/145—Maleic acid

Definitions

  • the invention relates to the technical field of renewable energy, in particular to a catalyst for catalyzing the oxidation of furfural to prepare maleic acid, and a preparation method and application thereof.
  • maleic acid As an important chemical raw material and intermediate, maleic acid is widely used in industry.
  • the main purpose of maleic acid is to manufacture unsaturated polyester resins, and it can also be used as a new type of sour agent in the food and beverage industry. By adding an appropriate amount of maleic acid, it can enhance the special fruit flavor and improve the taste. Maleic acid. Therefore, how to efficiently prepare maleic acid, especially using renewable resources to prepare maleic acid, has aroused widespread concern in various countries.
  • the problem to be solved by the present invention is that the existing method for preparing maleic acid requires the use of fossil products as raw materials for production, the reaction conditions are harsh, and the conversion rate of raw materials and the yield of maleic acid are low.
  • the invention provides a catalyst for catalytically oxidizing furfural to prepare maleic acid, which is composed of carbon nitride doped with potassium salt.
  • the potassium salt is one of potassium bromide, potassium chloride, and potassium nitrate
  • the precursor of carbon nitride is one of urea, dihydrodiamine, and melamine.
  • the mass ratio of the added amount of the potassium salt to the added amount of the precursor is 0.01- (0.2: 1).
  • the invention also provides a preparation method of the above catalyst, including the following steps:
  • step (3) The mixture dried in step (2) is calcined to obtain a catalyst.
  • the mixing temperature in the step (1) is room temperature, and the mixing and stirring time is 6-12h;
  • the drying temperature in the step (2) is 60-120 ° C, and the drying time is 8-12h;
  • a muffle furnace is used for calcination, the calcination temperature is 520-550 ° C, the calcination time is 2h, and the heating rate is 1-10 ° C / min.
  • the invention also provides the application of the above catalyst in the catalytic oxidation of furfural to prepare maleic acid, and the preparation method thereof is: carrying out catalytic oxidation reaction of furfural in a solvent.
  • the oxidant used in the oxidation reaction is one or more of hydrogen peroxide, potassium permanganate, potassium chlorate and oxygen.
  • the temperature of the catalytic furfural oxidation reaction is 60-120 ° C.
  • the mass ratio of the furfural to the catalyst is 1- (200: 1).
  • the ratio of the volume of the solvent to the mass of furfural is (1mL-50mL): 1mg.
  • the present invention avoids the use of fossil products such as butadiene and benzene, eases the pressure of the petroleum industry, directly uses furfural as a raw material, and has mild reaction conditions, which overcomes the traditional chemical synthesis method and the rigorous reaction required in the catalytic process
  • the shortcomings of the conditions, and less side reactions, green and pollution-free, can effectively reduce the initial investment cost, which is conducive to the sustainable development of environmental resources;
  • the catalyst prepared by the invention has strong catalytic selectivity, has the characteristics of recyclability and reuse, and is easy to separate from the product.
  • test materials and reagents used in the following examples can be obtained from commercial sources.
  • the preparation of a catalyst made of potassium bromide doped carbon nitride includes the following steps:
  • step (2) After drying the stirred solution in step (1) at 80 ° C, grind it into a powder and put it into a crucible with a lid;
  • step (3) The powder in step (2) was placed in a muffle furnace and calcined at 550 ° C for 2 hours to obtain a potassium bromide-doped carbon nitride catalyst.
  • the potassium bromide-doped carbon nitride prepared in this example was characterized. As a result, the surface basicity of the potassium bromide-doped carbon nitride was 1.61 mmol / g.
  • the preparation of a catalyst composed of potassium chloride doped carbon nitride includes the following steps:
  • step (2) After drying the stirred solution in step (1) at 80 ° C, grind it into a powder and put it into a crucible with a lid;
  • step (3) The powder in step (2) was placed in a muffle furnace and calcined at 550 ° C for 2 hours to obtain a potassium bromide-doped carbon nitride catalyst.
  • the preparation of a catalyst composed of potassium nitrate doped carbon nitride includes the following steps:
  • step (2) After drying the stirred solution in step (1) at 80 ° C, grind it into a powder and put it into a crucible with a lid;
  • step (3) The powder in step (2) was placed in a muffle furnace and calcined at 550 ° C for 2 hours to obtain a potassium bromide-doped carbon nitride catalyst.
  • the preparation of a carbon nitride catalyst includes the following steps:
  • step (2) After drying the stirred solution in step (1) at 80 ° C, grind it into a powder and put it into a crucible with a lid;
  • step (3) The powder in step (2) was placed in a muffle furnace and calcined at 550 ° C for 2 hours to obtain a carbon nitride catalyst.
  • the catalyst in Example 1 is used to catalyze the oxidation of furfural to prepare maleic acid.
  • the preparation method includes the following steps:
  • the component detection of the above filtrate showed that the main component of the liquid was maleic acid, and the yield of maleic acid was 70.40%;
  • the catalyst prepared in Example 2 is used to catalyze the oxidation of furfural to prepare maleic acid.
  • the preparation method includes the following steps:
  • the component detection of the above filtrate showed that the liquid components were maleic acid, furanone and succinic acid, and the yields were 21.12%, 26.19% and 22.41%, respectively;
  • the catalyst in Example 3 is used to catalyze the oxidation of furfural to prepare maleic acid.
  • the preparation method includes the following steps:
  • composition test of the above filtrate showed that the main components of the liquid were maleic acid, furanone and succinic acid, and the yields were 13.32%, 27.48% and 32.58%, respectively;
  • the catalyst in Example 4 is used to catalyze the oxidation of furfural to prepare maleic acid.
  • the preparation method includes the following steps:
  • composition test of the above filtrate showed that the main components of the liquid were maleic acid, furanone and succinic acid, and the yields were 16.82%, 27.01% and 24.72%, respectively;
  • the catalyst in Example 4 is used to catalyze the oxidation of furfural to prepare maleic acid.
  • the preparation method includes the following steps:
  • the catalyst in Example 1 is used to catalyze the oxidation of furfural to prepare maleic acid.
  • the preparation method includes the following steps:
  • the catalyst in Example 1 is used to catalyze the oxidation of furfural to prepare maleic acid.
  • the preparation method includes the following steps:
  • the catalyst in Example 1 is used to catalyze the oxidation of furfural to prepare maleic acid.
  • the preparation method includes the following steps:
  • maleic acid was prepared according to the preparation method of Example 2.
  • the filter residue obtained by filtration in the process of preparing maleic acid was dried and characterized.
  • the surface alkalinity of the filter residue was 1.52 mmol / g;
  • the yield of the prepared maleic acid product was tested, and the yield was 60.32% (under the condition that the catalyst was used for one cycle).
  • the catalyst residue used in the one-cycle test is replaced with the filter residue obtained from the one-cycle test, and maleic acid is prepared according to the preparation conditions of the one-cycle test.
  • the yield of the prepared maleic acid product was tested, and the yield was 55.82% (under the condition of using the catalyst for the second cycle);

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Abstract

一种催化氧化糠醛制备马来酸的催化剂及其制备方法和应用。该催化剂由钾盐掺杂的氮化碳构成。制备方法包括：将钾盐、氮化碳的前驱体、溶剂混合，烘干、煅烧后得到该催化剂。该催化剂在催化氧化糠醛制备马来酸中的应用，包括：在催化剂存在下，将糠醛在溶剂中进行氧化反应。糠醛转化率可达99％以上，马来酸收率最高可达70.40％。

Description

催化氧化糠醛制备马来酸的催化剂及其制备方法和应用 技术领域
本发明涉及可再生能源技术领域，具体涉及一种催化氧化糠醛制备马来酸的催化剂及其制备方法和应用。
背景技术
马来酸作为一种重要的化工原料和中间体，在工业上的应用十分广泛。马来酸的主要用途是制造不饱聚酯树脂，也可以作为食品饮料工业中的新型酸味剂，通过添加适量马来酸可增强特殊果香味并改善口感，目前全球每年大约需要180万吨的马来酸。因此，如何高效地制备马来酸，尤其是利用可再生资源制备马来酸，引起了各国的广泛关注。
马来酸的生产方法很多，但在工业上应用的方法主要是在五氧化二钒作为催化剂催化条件下，于450-500℃用空气氧化苯，先生成马来酸酐，经水解即可得到马来酸。此法的缺点在于使用了化石类产品，且反应条件非常苛刻，需要在高温高压下进行。
目前，使用可再生碳源替代化石类产品制备马来酸的技术引起了国内外的高度关注，同时也获得了快速发展，但目前国内外开展的可再生碳源制备马来酸研究中普遍存在着的原料转化率和产品收率低的问题。
发明内容
本发明所要解决的问题在于现有的制备马来酸的方法需要使用化石类产品作为生产原料，反应条件苛刻，原料转化率和马来酸的收率较低。
本发明是采用以下技术方案解决上述技术问题的：
本发明提供一种催化氧化糠醛制备马来酸的催化剂，由钾盐掺杂的氮化碳构成。
优选的，所述钾盐为溴化钾、氯化钾、硝酸钾中的一种，所述氮化碳的前驱体为尿素、二氢二胺和三聚氰胺中的一种。
优选的，所述钾盐的添加量与前驱体添加量的质量比0.01-(0.2:1)。
本发明还提供上述催化剂的制备方法，包括以下步骤：
(1)将钾盐、氮化碳的前驱体、溶剂混合；
(2)将步骤(1)中的混合物烘干；
(3)将步骤(2)中烘干的混合物进行煅烧，得到催化剂。
优选的，所述步骤(1)中的混合温度为室温，混合搅拌时间为6-12h；所述步骤(2)中 的烘干温度为60-120℃，烘干时间为8-12h；所述步骤(3)中采用马弗炉进行煅烧，煅烧温度为520-550℃，煅烧时间为2h，升温速率为1-10℃/min。
本发明还提供上述催化剂在催化氧化糠醛制备马来酸中的应用，其制备方法为：将糠醛在溶剂中进行催化氧化反应。
优选的，所述氧化反应采用的氧化剂为过氧化氢、高锰酸钾、氯酸钾和氧气中的一种或多种。
优选的，所述催化氧化糠醛反应的温度为60-120℃。
优选的，所述糠醛与催化剂的质量比为1-(200:1)。
优选的，所述溶剂的体积与糠醛的质量之比为(1mL-50mL):1mg。
本发明的有益效果在于：
(1)本发明避免了化石类产品如丁二烯、苯的利用，缓解了石油产业的压力，直接以糠醛为原料，反应条件温和，克服了传统的化学合成法和催化过程中需要苛刻反应条件的缺点，且副反应少，绿色无污染，可有效降低前期投入成本，利于环境资源的可持续发展；
(2)利用本发明的催化剂和制备方法催化氧化糠醛制备马来酸，具有较高的糠醛转化率和马来酸收率，糠醛转化率在99％以上，马来酸收率最高可达70.40％；
(3)本发明制备的催化剂催化选择性强，具有可回收重复利用的特点，易于从产物中分离。
具体实施方式
以下将结合实施例对本发明做进一步详细说明。
下述实施例中所用的试验材料和试剂等，如无特殊说明，均可从商业途径获得。
实施例1
溴化钾掺杂的氮化碳构成的催化剂的制备，包括以下步骤：
(1)取10g尿素和0.5g溴化钾，加入30g水溶液，室温搅拌均匀；
(2)将步骤(1)中搅拌后的溶液于80℃条件下烘干后，研磨成粉末，放入带有盖子的坩埚内；
(3)将步骤(2)中的粉末置于马弗炉中，550℃煅烧2h，获得溴化钾掺杂的氮化碳催化剂。
对本实施例中的制得的溴化钾掺杂的氮化碳进行表征，结果为：所述溴化钾掺杂的氮化 碳的表面碱度为1.61mmol/g。
实施例2
氯化钾掺杂的氮化碳构成的催化剂的制备，包括以下步骤：
(1)取10g尿素和0.5g氯化钾，加入30g水溶液，室温搅拌均匀；
(2)将步骤(1)中搅拌后的溶液于80℃条件下烘干后，研磨成粉末，放入带有盖子的坩埚内；
(3)将步骤(2)中的粉末置于马弗炉中，550℃煅烧2h，获得溴化钾掺杂的氮化碳催化剂。
实施例3
硝酸钾掺杂的氮化碳构成的催化剂的制备，包括以下步骤：
(1)取10g尿素和0.5g硝酸钾，加入30g水溶液，室温搅拌均匀；
(2)将步骤(1)中搅拌后的溶液于80℃条件下烘干后，研磨成粉末，放入带有盖子的坩埚内；
(3)将步骤(2)中的粉末置于马弗炉中，550℃煅烧2h，获得溴化钾掺杂的氮化碳催化剂。
实施例4
氮化碳构成的催化剂的制备，包括以下步骤：
(1)取10g尿素，加入30g水溶液，室温搅拌均匀；
(2)将步骤(1)中搅拌后的溶液于80℃条件下烘干后，研磨成粉末，放入带有盖子的坩埚内；
(3)将步骤(2)中的粉末置于马弗炉中，550℃煅烧2h，获得氮化碳催化剂。
实施例5
利用实施例1中的催化剂催化氧化糠醛制备马来酸，其制备方法包括以下步骤：
取1mmol糠醛，50mg实施例1中制得的溴化钾掺杂的氮化碳，4mL去离子水，置于厚壁耐压管中，再加入1mL 30％过氧化氢溶液；厚壁耐压管中放入磁力搅拌子，将上述溶液放入油浴锅中，使其转速为500rpm，将温度升温至100℃后停留3h；反应结束后立即取出厚壁耐压管于空气中降至室温；将反应液从反应釜中转移出，过滤，过滤得到的滤渣(溴化钾掺杂的氮化碳)烘干备用；过滤得到的滤液则用于成分检测，另一部分进行蒸发再结晶，得到 白色固体，即为马来酸制品。
实验结果：
对上述滤液进行成分检测，结果表明该液体主要成分为马来酸，马来酸收率为70.40％；
对滤液稀释20倍后，使用Waters 515 HPLC(高效液相色谱)进行测量分析，结果显示，本实施例中糠醛的转化率在99％以上。
实施例6
利用实施例2中制备的催化剂催化氧化糠醛制备马来酸，其制备方法包括以下步骤：
取1mmol糠醛，50mg实施例2中制得的氯化钾掺杂的氮化碳，4mL去离子水，置于厚壁耐压管中，再加入1mL 30％过氧化氢溶液；厚壁耐压管中放入磁力搅拌子，将上述溶液放入油浴锅中，使其转速为500rpm，将温度升温至100℃后停留3h；反应结束后立即取出厚壁耐压管于空气中降至室温；将反应液从反应釜中转移出，过滤，过滤得到的滤渣烘干备用；过滤得到的滤液则用于成分检测，另一部分进行蒸发再结晶，得到白色固体，即为马来酸制品。
实验结果：
对上述滤液进行成分检测，结果表明该液体成分为马来酸、呋喃酮和丁二酸，收率分别为21.12％、26.19％和22.41％；
对滤液稀释20倍后，使用Waters 515 HPLC(高效液相色谱)进行测量分析。结果显示，本实施例中糠醛的转化率在99％以上。
实施例7
利用实施例3中的催化剂催化氧化糠醛制备马来酸，其制备方法包括以下步骤：
取1mmol糠醛，50mg实施例3中制得的硝酸钾掺杂的氮化碳，4mL去离子水，置于厚壁耐压管中，再加入1mL 30％过氧化氢溶液；厚壁耐压管中放入磁力搅拌子，将上述溶液放入油浴锅中，使其转速为500rpm，将温度升温至100℃后停留3h；反应结束后立即取出厚壁耐压管于空气中降至室温；将反应液从反应釜中转移出，过滤，过滤得到的滤渣(硝酸钾掺杂的氮化碳)烘干备用；过滤得到的滤液则用于成分检测，另一部分进行蒸发再结晶，得到白色固体，即为马来酸制品。
实验结果：
对上述滤液进行成分检测，结果表明该液体主要成分为马来酸、呋喃酮和丁二酸，收率 分别为13.32％、27.48％和32.58％；
对滤液稀释20倍后，使用Waters 515 HPLC(高效液相色谱)进行测量分析，结果显示，本实施例中糠醛的转化率在99％以上。
实施例8
利用实施例4中的催化剂催化氧化糠醛制备马来酸，其制备方法包括以下步骤：
取1mmol糠醛，50mg实施例4中制得的氮化碳，4mL去离子水，置于厚壁耐压管中，再加入1mL 30％过氧化氢溶液；厚壁耐压管中放入磁力搅拌子，将上述溶液放入油浴锅中，使其转速为500rpm，将温度升温至100℃后停留3h；反应结束后立即取出厚壁耐压管于空气中降至室温；将反应液从反应釜中转移出，过滤，过滤得到的滤渣(氮化碳)烘干备用；过滤得到的滤液则用于成分检测，另一部分进行蒸发再结晶，得到白色固体，即为马来酸制品。
实验结果：
对上述滤液进行成分检测，结果表明该液体主要成分为马来酸、呋喃酮和丁二酸，收率分别为16.82％、27.01％和24.72％；
对滤液稀释20倍后，使用Waters 515 HPLC(高效液相色谱)进行测量分析，结果显示，本实施例中糠醛的转化率在99％以上。
实施例9
利用实施例4中的催化剂催化氧化糠醛制备马来酸，其制备方法包括以下步骤：
取1mmol糠醛，25mg实施例4中制得的氮化碳和25mg溴化钾，4mL去离子水，置于厚壁耐压管中，再加入1mL 30％过氧化氢溶液；厚壁耐压管中放入磁力搅拌子，将上述溶液放入油浴锅中，使其转速为500rpm，将温度升温至100℃后停留3h；反应结束后立即取出厚壁耐压管于空气中降至室温；将反应液从反应釜中转移出，过滤，过滤得到的滤渣(氮化碳)烘干备用；过滤得到的滤液则用于成分检测，另一部分进行蒸发再结晶，得到白色固体，即为马来酸制品。
实验结果：
对上述滤液进行成分检测，结果表明该液体主要成分为马来酸收率分别为47.31％；
对滤液稀释20倍后，使用Waters 515 HPLC(高效液相色谱)进行测量分析，结果显示，本实施例中糠醛的转化率在99％以上。
实施例10
利用实施例1中的催化剂催化氧化糠醛制备马来酸，其制备方法包括以下步骤：
取1mmol糠醛，50mg实施例1中制得溴化钾掺杂的氮化碳，4mL去离子水，置于厚壁耐压管中，再加入1mL 30％过氧化氢溶液；厚壁耐压管中放入磁力搅拌子，将上述溶液放入油浴锅中，使其转速为500rpm，将温度升温至100℃后停留30min；反应结束后立即取出厚壁耐压管于空气中降至室温；将反应液从反应釜中转移出，过滤，过滤得到的滤渣(溴化钾掺杂的氮化碳)烘干备用；过滤得到的滤液则用于成分检测，另一部分进行蒸发再结晶，得到白色固体，即为马来酸制品。
实验结果：
对上述滤液进行成分检测，结果为：该液体主要成分为马来酸收率分别为27.32％；
对滤液稀释20倍后，使用Waters 515 HPLC(高效液相色谱)进行测量分析，结果显示，本实施例中糠醛的转化率在40％左右。
实施例11
利用实施例1中的催化剂催化氧化糠醛制备马来酸，其制备方法包括以下步骤：
取1mmol糠醛，50mg实施例1中制得溴化钾掺杂的氮化碳，4mL去离子水，置于厚壁耐压管中，再加入1mL 30％过氧化氢溶液；厚壁耐压管中放入磁力搅拌子，将上述溶液放入油浴锅中，使其转速为500rpm，将温度升温至100℃后停留60min；反应结束后立即取出厚壁耐压管于空气中降至室温；将反应液从反应釜中转移出，过滤，过滤得到的滤渣(溴化钾掺杂的氮化碳)烘干备用；过滤得到的滤液则用于成分检测，另一部分进行蒸发再结晶，得到白色固体，即为马来酸制品。
实验结果：
对上述滤液进行成分检测，结果为：该液体主要成分为马来酸收率分别为45.36％；
对滤液稀释20倍后，使用Waters 515 HPLC(高效液相色谱)进行测量分析，结果显示，本实施例中糠醛的转化率在63％左右。
实施例12
利用实施例1中的催化剂催化氧化糠醛制备马来酸，其制备方法包括以下步骤：
取1mmol糠醛，50mg实施例1中制得溴化钾掺杂的氮化碳，4mL去离子水，置于厚壁耐压管中，再加入1mL 30％过氧化氢溶液；厚壁耐压管中放入磁力搅拌子，将上述溶液放 入油浴锅中，使其转速为500rpm，将温度升温至100℃后停留120min；反应结束后立即取出厚壁耐压管于空气中降至室温；将反应液从反应釜中转移出，过滤，过滤得到的滤渣(溴化钾掺杂的氮化碳)烘干备用；过滤得到的滤液则用于成分检测，另一部分进行蒸发再结晶，得到白色固体，即为马来酸制品。
实验结果：
对上述滤液进行成分检测，结果为：该液体主要成分为马来酸收率分别为50.32％；
对滤液稀释20倍后，使用Waters 515 HPLC(高效液相色谱)进行测量分析，结果显示，本实施例中糠醛的转化率在75％左右。
实施例13
溴化钾掺杂的氮化碳的循环性能测试
(1)一次循环测试
将上述滤渣替换实施例2使用的溴化钾掺杂的氮化碳作为催化剂，按照实施例2的制备方法制备马来酸。
实验结果：
将制备马来酸过程中过滤得到的滤渣烘干后进行表征，滤渣的表面碱度为1.52mmol/g；
对制得的马来酸制品的收率进行检测，收率为60.32％(催化剂一次循环使用条件下)。
(2)二次循环测试
以一次循环测试得到的滤渣替换一次循环测试使用的催化剂，按照一次循环测试的制备条件制备马来酸。
实验结果：
对制得的马来酸制品的收率进行检测，收率为55.82％(催化剂二次循环使用条件下)；
将在制备马来酸过程中过滤得到的滤液稀释20倍后，使用Waters 515 HPLC(高效液相色谱仪)进行测量分析，结果显示，本实施例中糠醛的转化率为85％。
通过一次和二次循环测试的结果可以看出，本发明实施例1制得的催化剂的循环使用性能良好。
以上仅是本发明的优选实施方式，本发明的保护范围并不仅局限于上述实施例，与本发明构思无实质性差异的各种工艺方案均在本发明的保护范围内。

Claims (10)

  1. 一种催化氧化糠醛制备马来酸的催化剂，其特征在于：由钾盐掺杂的氮化碳构成。
  2. 根据权利要求1所述的催化氧化糠醛制备马来酸的催化剂，其特征在于：所述钾盐为溴化钾、氯化钾、硝酸钾中的一种，所述氮化碳的前驱体为尿素、二氢二胺和三聚氰胺中的一种。
  3. 根据权利要求1所述的催化氧化糠醛制备马来酸的催化剂，其特征在于：所述钾盐的添加量与前驱体添加量的质量比0.01-(0.2:1)。
  4. 根据权利要求1-3中任一项所述的催化剂的制备方法，其特征在于：包括以下步骤：
    (1)将钾盐、氮化碳的前驱体、溶剂混合；
    (2)将步骤(1)中的混合物烘干；
    (3)将步骤(2)中烘干的混合物进行煅烧，得到催化剂。
  5. 根据权利要求4所述的催化剂的制备方法，其特征在于：所述步骤(1)中的混合温度为室温，混合搅拌时间为6-12h；所述步骤(2)中的烘干温度为60-120℃，烘干时间为8-12h；所述步骤(3)中采用马弗炉进行煅烧，煅烧温度为520-550℃，煅烧时间为2h，升温速率为1-10℃/min。
  6. 根据权利要求1-3中任一项所述的催化剂在催化氧化糠醛制备马来酸中的应用，其特征在于：其制备方法为：将糠醛在溶剂中进行催化氧化反应。
  7. 根据权利要求6所述的催化剂在催化氧化糠醛制备马来酸中的应用，其特征在于：所述氧化反应采用的氧化剂为过氧化氢、高锰酸钾、氯酸钾和氧气中的一种或多种。
  8. 根据权利要求6所述的催化剂在催化氧化糠醛制备马来酸中的应用，其特征在于：所述催化氧化糠醛反应的温度为60-120℃。
  9. 根据权利要求6所述的催化剂在催化氧化糠醛制备马来酸中的应用，其特征在于：所述糠醛与催化剂的质量比为1-(200:1)。
  10. 根据权利要求6所述的催化剂在催化氧化糠醛制备马来酸中的应用，其特征在于：所述溶剂的体积与糠醛的质量之比为(1mL-50mL):1mg。
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