A catalyst for preparing hydroxyfructose acid and a preparation method and application thereof

Abstract

The application provides a catalyst for preparing hydroxyl fructosacetic acid and a preparation method and application thereof, and relates to the technical field of hydroxyl fructosacetic acid. The catalyst is prepared from a soluble salt of M, a soluble nitrate and KI as raw materials through the action of an alkaline precipitant to obtain a finished catalyst. The catalyst is used for the preparation of hydroxyl fructosacetic acid, the use of the catalyst can avoid the introduction of a large amount of alkaline medium in the preparation of fructosacetic acid and the generation of toxic by-products, the whole process is green and environmentally friendly, the preparation process is simple and convenient, the conversion rate of the substrate is up to 95% or more, and the yield of fructosacetic acid can reach 79%.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of hydroxyl fructosic acid, and particularly relates to a catalyst for preparing hydroxyl fructosic acid and a preparation method and application thereof. BACKGROUND

[0002] Fructosic acid is a very important high-value chemical, mainly including glycolic acid, tartaric acid, glyceric acid, levulinic acid, lactic acid, etc., and is widely applied to food, cosmetics and medicine fields and has important regulating effects in vivo.

[0003] Natural fructosic acid exists in vegetable and fruit foods, but the content is very low. In the prior art, there are three kinds of synthesis processes of fructosic acid, namely, coal chemical synthesis, biological fermentation and chemical oxidation, but these synthesis processes all have inevitable shortcomings. In the coal chemical synthesis process, the coal refining process is too complex, the energy consumption is very high, the by-product has low added value, and the environment is polluted at the same time; the biological fermentation process has disadvantages of long production cycle, many by-products, complex synthesis of fermentation strains, and the like, and the strains are adsorbed on the membrane, which reduces the service life of the membrane and increases the cost; in the chemical oxidation process for preparing fructosic acid, a noble metal catalyst is usually used and an alkaline medium is introduced in the reaction process, so the process has corresponding shortcomings of high cost and serious pollution.

[0004] Therefore, it is of great significance to develop a new green synthesis method of fructosic acid to overcome the many problems existing in the synthesis processes of fructosic acid. SUMMARY

[0005] To solve the above problems, the present application provides a catalyst for preparing hydroxyl fructosic acid, and the preparation of fructosic acid under the catalysis of the catalyst can significantly improve the conversion rate of raw materials, reduce the generation of by-products, simplify the preparation process of fructosic acid and reduce the preparation cost of fructosic acid.

[0006] The preparation method of the catalyst for preparing hydroxyl fructosic acid provided by the present application comprises the following steps:

[0007] S1, dissolving a soluble salt of a precursor M, a soluble nitrate and KI in a solvent to obtain a mixed solution A;

[0008] S2, dissolving an alkaline precipitant in deionized water to obtain a solution B;

[0009] S3, titrating and mixing the solution A and the solution B at room temperature and adjusting the pH to 4-8 to obtain a slurry C;

[0010] S4, transferring the slurry C to a Teflon-lined stainless steel hydrothermal reaction kettle, heating and keeping warm, and naturally cooling to room temperature after keeping warm is finished;

[0011] S5, centrifuging the cooled slurry C, washing the filter cake obtained after centrifugation with deionized water and centrifuging three times, and drying to obtain the finished catalyst.

[0012] Further, the M is one or more of Mn, Fe, Ni, Co, Au, P, Pd.

[0013] Further, the soluble nitrate is one or more of Bi(NO3)3·5H2O, Zr(NO3)2, Ce(NO3)2.

[0014] Further, the solvent is one or more of NaOH, NaHCO3, Na2CO3.

[0015] Further, the concentration of M in the mixed solution A is 0.07 mol / L, 0.11 mol / L or 0.14 mol / L, the concentration of the soluble nitrate is 0.07 mol / L, and the concentration of KI is 0.14 mol / L.

[0016] Further, the alkaline precipitant is one or more of NaOH, NaHCO3, Na2CO3.

[0017] Further, the concentration of the alkaline precipitant in the solution B is 0.1-5 mol / L.

[0018] Further, the pH value of the slurry C is 4, 5, 6, 7 or 8.

[0019] Further, the holding temperature is 160℃, and the holding time is 2h.

[0020] Further, the centrifugal speed is 9000r / min, and the centrifugal time is 5min.

[0021] Further, the drying temperature is 70℃-110℃, and the drying time is 8-24h. Preferably, the drying temperature is 70℃, 90℃ or 110℃, and the drying time is 8h, 16h or 24h.

[0022] Further, the content of M in the finished catalyst is 0.1wt%-30wt%.

[0023] The application also provides a catalyst product prepared according to the above method.

[0024] The catalyst provided by the application is used for preparing hydroxyl fructosyl acid, and the specific method is as follows:

[0025] The reaction substrate is mixed with the catalyst in proportion, and then the reaction is carried out to obtain hydroxyl fructosyl acid.

[0026] Further, the reaction substrate is one or more of cellulose, hemicellulose, cellobiose, arabinose, erythrose, mannose, glucose, fructose, and xylose.

[0027] Further, the concentration of the reaction substrate is 0.1-0.5 mol / L.

[0028] Further, the molar ratio of the metal catalyst to the reaction substrate is 1:5-35.

[0029] Further, the reaction temperature is 120-200°C, and the reaction time is 1-10 h.

[0030] Further, the preparation process of hydroxymalic acid is a batch process, and the oxygen pressure is 10 bar.

[0031] Compared with the prior art, the present application has the beneficial technical effects of:

[0032] The present application uses a specific catalyst to avoid the introduction of a large amount of alkaline medium and the generation of toxic by-products during the preparation of fructose acid, and the entire process is green and environmentally friendly. The preparation process is simple and convenient, the conversion rate of the substrate is as high as 95% or more, and the yield of fructose acid can reach 79%. DETAILED DESCRIPTION

[0033] The technical solutions provided by the present application are further described below in conjunction with examples.

[0034] Example 1 Preparation of 1.5Mn / BiOI(H2O) catalyst

[0035] S1, dissolve the precursors Mn(NO3)2, Bi(NO3)3, and KI in water to obtain a mixed solution A, the concentration of Mn(NO3)2 in solution A is 0.11 mol / L, the concentration of Bi(NO3)3 is 0.07 mol / L, and the concentration of KI is 0.14 mol / L;

[0036] S2, dissolve NaOH in deionized water to obtain solution B, the molar concentration of solution B is 1 mol / L;

[0037] S3, under room temperature conditions, titrate and mix solution A and solution B and adjust the pH to 6 to obtain slurry C;

[0038] S4, transfer slurry C to a Teflon-lined stainless steel autoclave, heat to 160°C and keep for 2 h, and then naturally cool to room temperature after the incubation is completed;

[0039] S5, centrifuge the cooled slurry C, wash the filter cake obtained after centrifugation with deionized water three times, and then dry, dry at 160°C for 2 h to obtain the finished product 1.5Mn / BiOI(H2O) catalyst.

[0040] Example 2 Preparation of 1.5Mn / BiOI (GLY) catalyst

[0041] The same as example 1, except that:

[0042] S1, the precursor Mn(NO3)2and Bi(NO3)3, KI are co-dissolved in glycerol to obtain a mixed solution A, the concentration of Mn(NO3)2contained in solution A is 0.11 mol / L, the concentration of Bi(NO3)3is 0.07 mol / L, and the concentration of KI is 0.14 mol / L.

[0043] Example 3 Preparation of 1.5Mn / BiOI (EG) catalyst

[0044] The same as example 1, except that:

[0045] S1, the precursor Mn(NO3)2and Bi(NO3)3, KI are co-dissolved in glycerol to obtain a mixed solution A, the concentration of Mn(NO3)2contained in solution A is 0.11 mol / L, the concentration of Bi(NO3)3is 0.07 mol / L, and the concentration of KI is 0.14 mol / L.

[0046] Example 4 Preparation of 1.5Mn / BiOI (IPA) catalyst

[0047] The same as example 1, except that:

[0048] S1, the precursor Mn(NO3)2and Bi(NO3)3, KI are co-dissolved in glycerol to obtain a mixed solution A, the concentration of Mn(NO3)2contained in solution A is 0.11 mol / L, the concentration of Bi(NO3)3is 0.07 mol / L, and the concentration of KI is 0.14 mol / L.

[0049] Example 5 Preparation of 1.5Mn / BiOI (ETOH) catalyst

[0050] The same as example 1, except that:

[0051] S1, the precursor Mn(NO3)2and Bi(NO3)3, KI are co-dissolved in glycerol to obtain a mixed solution A, the concentration of Mn(NO3)2contained in solution A is 0.11 mol / L, the concentration of Bi(NO3)3is 0.07 mol / L, and the concentration of KI is 0.14 mol / L.

[0052] Example 6 Preparation of Pt / BiOI (H2O) catalyst

[0053] The same as example 1, except that:

[0054] S1, the precursor H2PtCl6·6H2O is co-dissolved with Bi(NO3)3, KI in water to obtain a mixed solution A, the concentration of H2PtCl6·6H2O contained in solution A is 0.07 mol / L, the concentration of Bi(NO3)3 is 0.07 mol / L, and the concentration of KI is 0.14 mol / L.

[0055] Example 7 Preparation of Au / BiOI(H2O) catalyst

[0056] The same as example 1, except that:

[0057] S1, the precursor HAuCl4·4H2O is co-dissolved with Bi(NO3)3, KI in water to obtain a mixed solution A, the concentration of HAuCl4·4H2O contained in solution A is 0.07 mol / L, the concentration of Bi(NO3)3 is 0.07 mol / L, and the concentration of KI is 0.14 mol / L.

[0058] Example 8 Preparation of Fe / BiOI(H2O) catalyst

[0059] The same as example 1, except that:

[0060] S1, the precursor Fe(NO3)3 is co-dissolved with Bi(NO3)3, KI in water to obtain a mixed solution A, the concentration of Fe(NO3)3 contained in solution A is 0.07 mol / L, the concentration of Bi(NO3)3 is 0.07 mol / L, and the concentration of KI is 0.14 mol / L.

[0061] Example 9 Preparation of Co / BiOI(EG) catalyst

[0062] The same as example 1, except that:

[0063] S1, the precursor Co(NO3)2·6H2O is co-dissolved with Bi(NO3)3, KI in ethylene glycol to obtain a mixed solution A, the concentration of Co(NO3)2·6H2O contained in solution A is 0.11 mol / L, the concentration of Bi(NO3)3 is 0.07 mol / L, and the concentration of KI is 0.14 mol / L.

[0064] Example 10 Preparation of Ni / BiOI(H2O) catalyst

[0065] The same as example 1, except that:

[0066] S1, dissolve the precursors Ni(NO3)2, Bi(NO3)3 and KI in water to obtain a mixed solution A, the concentration of Ni(NO3)2 in solution A is 0.07 mol / L, the concentration of Bi(NO3)3 is 0.07 mol / L, and the concentration of KI is 0.14 mol / L.

[0067] Example 11 Preparation of Mn / Bi2O3 catalyst

[0068] The same as Example 1, except that:

[0069] S1, dissolve the precursors Mn(NO3)2 and Bi(NO3)3 in water to obtain a mixed solution A, the concentration of Mn(NO3)2 in solution A is 0.07 mol / L, and the concentration of Bi(NO3)3 is 0.14 mol / L.

[0070] Example 12 Preparation of Mn / ZrO2 catalyst

[0071] S1, dissolve the precursors Mn(NO3)2 and Zr(NO3)4 in water to obtain a mixed solution A, the concentration of Mn(NO3)2 in solution A is 0.07 mol / L, and the concentration of Zr(NO3)4 is 0.07 mol / L.

[0072] S2, dissolve NaOH in deionized water to obtain solution B, the molar concentration of solution B is 1 mol / L;

[0073] S3, under room temperature conditions, titrate and mix solution A and solution B and adjust the pH to 7 to obtain slurry C;

[0074] S4, transfer slurry C to a Teflon-lined stainless steel autoclave, heat to 160°C and keep for 2h, and then naturally cool to room temperature after the heat preservation is completed;

[0075] S5, centrifuge the cooled slurry C, wash the filter cake obtained after centrifugation with deionized water three times and dry, and then dry at 160°C for 2h to obtain the finished Mn / ZrO2 catalyst.

[0076] Example 13 Preparation of Pd / BiOI(H2O) catalyst

[0077] The same as Example 1, except that:

[0078] S1, dissolve the precursors Pd(NO3)2·2H2O, Bi(NO3)3 and KI in water to obtain a mixed solution A, the concentration of Pd(NO3)2·2H2O in solution A is 0.07 mol / L, the concentration of Bi(NO3)3 is 0.07 mol / L, and the concentration of KI is 0.14 mol / L.

[0079] Test Example 1 Glucose Oxidation Reaction Experiment

[0080] The number before the metal is the metal loading amount, and the substance in the parentheses is the solvent used in the process of preparing the catalyst.

[0081] Reaction conditions: 0.1 mol / L glucose 15 mL, 0.05 g of catalyst, water as a solvent, 10 bar of oxygen pressure. GLY: glycerol, EG: ethylene glycol, GA: glycolic acid, GLYA: glyceric acid, FA: formic acid, TA: tartaric acid, LeA: levulinic acid, LA: lactic acid, Others: arabonic acid, erythritol, 5-hydroxymethylfurfural, carbon dioxide, and the like.

[0082]

[0083] Test Example 2 Fructose Oxidation Reaction Experiment

[0084] The number before the metal is the metal loading amount, and the substance in the parentheses is the solvent used in the process of preparing the catalyst.

[0085] Reaction conditions: 0.1 mol / L fructose 15 mL, 0.05 g of catalyst, water as a solvent, 10 bar of oxygen pressure. Others: arabonic acid, erythritol, 5-hydroxymethylfurfural, carbon dioxide, and the like.

[0086]

[0087] Test Example 3 Cellulose Oxidation Reaction Experiment

[0088] The number before the metal is the metal loading amount, and the substance in the parentheses is the solvent used in the process of preparing the catalyst.

[0089] Reaction conditions: 0.1 mol / L fructose 15 mL, 0.05 g of catalyst, water as a solvent, 10 bar of oxygen pressure. IPA: isopropyl alcohol, ETOH: ethanol, Others: arabonic acid, erythritol, 5-hydroxymethylfurfural, carbon dioxide, and the like.

[0090]

[0091]

[0092] Test Example 4 Xylose Oxidation Reaction Experiment

[0093] The number before the metal is the metal loading amount, and the substance in the parentheses is the solvent used in the process of preparing the catalyst.

[0094] Reaction conditions: 0.1 mol / L fructose 15 mL, 0.05 g catalyst, water as solvent, 10 bar oxygen pressure. GLC: glucose, Others: arabinonic acid, erythritol, 5-hydroxymethylfurfural, carbon dioxide and the like.

[0095]

[0096] Test Example 5 Mannose oxidation reaction experiment

[0097] The number before the metal is the metal loading amount, and the substance in the bracket is the solvent used in the preparation of the catalyst.

[0098] Reaction conditions: 0.1 mol / L fructose 15 mL, 0.05 g catalyst, water as solvent, 10 bar oxygen pressure. GLC: glucose, Others: arabinonic acid, erythritol, 5-hydroxymethylfurfural, carbon dioxide and the like.

[0099]

[0100]

[0101] From Test Examples 1-5, it can be seen that the conversion rate of the method described in the present application is high, which can reach more than 95%, and the yield of fructose acid can reach 79%.

[0102] The principles and implementation modes of the present application are described by applying specific examples in this paper, and the above examples are only used to help understand the method of the present application and its core idea; at the same time, for those skilled in the art, according to the idea of the present application, there will be changes in the specific implementation mode and application range. In summary, the content of the specification should not be understood as a limitation of the present application.

Claims

1. A process for the preparation of hydroxyfructosyl acid, characterized in that, The method comprises the following steps: S1, dissolving the soluble salt of the precursor M, the soluble nitrate, and KI in a solvent to obtain a mixed solution A; S2, dissolving the alkaline precipitant in deionized water to obtain a solution B; S3, titrating and mixing the solution A and the solution B at room temperature and adjusting the pH to 4-8 to obtain a slurry C; S4, transferring the slurry C to a Teflon-lined stainless steel autoclave, heating, and then naturally cooling to room temperature after the heat preservation is completed; S5, centrifuging the cooled slurry C, washing and centrifuging the obtained filter cake three times with deionized water, and then drying to obtain a finished catalyst; The catalyst is used in a method for preparing hydroxyl fructose acid as follows: Mixing the reaction substrate with the catalyst in a proper proportion and then performing a reaction to obtain hydroxyl fructose acid; The reaction substrate is one or more of cellulose, hemicellulose, cellobiose, arabinose, erythrose, mannose, glucose, fructose, and xylose; the concentration of the reaction substrate is 0.1-0.5 mol / L; the molar ratio of the metal catalyst to the reaction substrate is 1:5-35; the reaction temperature is 120-200℃, and the reaction time is 1-10 h; the hydroxyl fructose acid preparation process is an intermittent process, and the oxygen pressure is 10 bar; The hydroxyl fructose acid is glycolic acid, glyceric acid, tartaric acid, levulinic acid, and lactic acid; The M is one or more of Mn, Fe, Ni, Co, Au, Pt, and Pd; The soluble nitrate is one or more of Bi(NO3)3·5H2O, Zr(NO3)2, and Ce(NO3)2; The solvent is water, glycerol, ethylene glycol, isopropyl alcohol, or ethanol; The content of M in the finished catalyst is 0.1wt%-30wt%.

2. The production method according to claim 1, characterized by, The alkaline precipitant is one or more of NaOH, NaHCO3, and Na2CO3.

3. The production method according to claim 1, characterized by, The concentration of the alkaline precipitant in the solution B is 0.1-5 mol / L.

4. The preparation method according to claim 1, characterized in that, The drying temperature is 70-110℃, and the drying time is 8-24 h.

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