A method for improving the storage and transportation stability of 5-hydroxymethylfurfural

Abstract

The present application discloses a method for improving the storage and transportation stability of 5-hydroxymethylfurfural, comprising: improving the storage and transportation stability of 5-hydroxymethylfurfural by a reducing environment within a pH range of 5 to 8; wherein the reducing environment comprises: adding a trace amount of reducing substance A, or adding a reducing substance B and a trace amount of metal ions; the reducing substance A comprises SO4 2‑ 、HSO3 ‑ The reducing substance B is an alcohol compound. The method eliminates free radical substances in the 5-hydroxymethylfurfural storage solution / solid or prevents the generation of free radicals, prevents the 5-hydroxymethylfurfural from undergoing side reactions such as polymerization or decomposition, and achieves the purpose of extending the storage and transportation time of the 5-hydroxymethylfurfural. The present invention has practical application value for the storage and transportation of 5-hydroxymethylfurfural.

Description

Technical Field

[0001] The present application relates to a method for improving the storage and transportation stability of 5-hydroxymethylfurfural, and belongs to the technical field of biomass chemical industry. Background Art

[0002] 5-Hydroxymethylfurfural (HMF) has been one of the research hotspots of bio-based chemicals in the past 20 years. It can be widely used in medicine, pesticides, fragrances, chemicals and other fields. As an important bio-based platform compound, HMF is expected to become a bulk chemical raw material in the future. However, HMF is unstable and is prone to chemical changes during storage and transportation, which directly affects subsequent applications. The instability of HMF is mainly due to the double bonds of aldehyde, hydroxymethyl and furan rings. It also contains trace impurities and free radicals generated by uneven cleavage of covalent bonds, which makes HMF prone to side reactions such as polymerization or degradation. Therefore, it is necessary to explore a method to improve the stability of HMF during storage and transportation to avoid HMF degradation, polymerization, discoloration, precipitation, agglomeration and other consequences caused by impurities, storage time, storage temperature, exposure, shaking, etc. At present, relevant protective formulas and applicable conditions have not been reported. Summary of the invention

[0003] According to one aspect of the present application, a method for improving the storage and transportation stability of 5-hydroxymethylfurfural is provided. The method utilizes the reducing property of a trace reducing compound itself, or forms a reducing environment under the catalytic action of a very trace amount of metal ions, eliminates free radical substances in a 5-hydroxymethylfurfural (HMF) storage solution / solid, prevents HMF from undergoing side reactions such as polymerization or decomposition, and achieves the purpose of improving the storage and transportation stability of HMF.

[0004] The method described in the present application utilizes the reducing property of trace reducing compounds themselves, or forms a reducing environment under the catalytic action of extremely trace metal ions, eliminates free radical substances in the HMF storage solution / solid or prevents the generation of free radicals, prevents HMF from undergoing side reactions such as polymerization or decomposition, and achieves the purpose of extending the storage and transportation time of HMF. The present invention has practical application value for the storage and transportation of HMF.

[0005] The main principle of the present invention is to utilize the reducing properties of compounds such as potassium bisulfite and 2-tert-butyl-6-methylphenol and the reaction between alcohol and Fe 2+ The reducing environment formed by metal ions protects the aldehyde groups in HMF from oxidation and degradation, and quenches the free radicals generated by HMF due to light, heating, vibration, impurities and other comprehensive factors, preventing HMF from polymerization, discoloration, agglomeration, etc.

[0006] The method for improving the storage and transportation stability of 5-hydroxymethylfurfural comprises: improving the storage and transportation stability of 5-hydroxymethylfurfural by using a reducing environment within a pH range of 5 to 8;

[0007] Wherein, the reducing environment includes: adding a slight reducing substance A, or adding a reducing substance B and a trace amount of metal ions;

[0008] The reducing substance A includes SO4 2- 、HSO3 - At least one of a phenolic compound and a diisocyanate compound;

[0009] The reducing substance B is an alcohol compound.

[0010] As one specific implementation method, the method for improving the storage and transportation stability of 5-hydroxymethylfurfural comprises: within a certain pH range, by adding a trace amount of reducing substance A, or adding a reducing substance B and a trace amount of metal ions with catalytic function, to improve the stability of 5-hydroxymethylfurfural during storage and transportation;

[0011] Wherein, the reducing substance A includes SO4 2- 、HSO3 - At least one of a phenolic compound and a diol compound;

[0012] Wherein, the reducing substance B is an alcohol compound.

[0013] As one specific embodiment, when the reducing substance A is SO4 2- When the compound is a reducing metal, the metal is a reducing metal such as iron, tin, cerium, titanium, etc.

[0014] Optionally, the SO4 2- The compound includes at least one of ferrous sulfate, stannous sulfate, cerous sulfate and titanium sulfate; the HSO3 - The compound includes at least one of sodium bisulfite, potassium bisulfite, and ammonium bisulfite.

[0015] Optionally, the phenol compound includes at least one of 2,6-di-tert-butyl-p-cresol (BHT), 2-tert-butyl-6-methylphenol, 4-methoxyphenol (MEHQ), tert-butylhydroquinone (TBHQ), butylated hydroxyanisole (BHA), and 2,4-dimethyl-6-tert-butylphenol.

[0016] Optionally, the SO4 2- 、HSO3 -When the phenol compound is added alone, the addition amount is 20 to 500 ppm; when the phenol compound is added alone, the addition amount is 20 to 400 ppm; the SO4 2- 、HSO3 - When the phenol compound and the phenol compound are mixed and added, the added amount is 20 to 300 ppm.

[0017] Optionally, the SO4 2- 、HSO3 - The amount of compounds added is 50 to 500 ppm.

[0018] Optionally, the SO4 2- 、HSO3 - The upper limit of the amount of the compound added is selected from 30ppm, 50ppm, 60ppm, 100ppm, 150ppm, 200ppm, 400ppm or 500ppm; the lower limit is selected from 20ppm, 30ppm, 50ppm, 60ppm, 100ppm, 150ppm, 200ppm or 400ppm.

[0019] Optionally, the SO4 2- 、HSO3 - The total amount of the mixed addition of the phenolic compound and the phenolic compound is any value of 20ppm, 30ppm, 60ppm, 200ppm, 300ppm and any point value between any two of the range values.

[0020] Optionally, the alcohol compound includes at least one of C1 to C8 alcohols.

[0021] Optionally, the alcohol compound is a monohydric alcohol compound, preferably a C1-C8 monohydric alcohol.

[0022] Optionally, the C1-C8 alcohol includes at least one of methanol, ethanol, propanol, isopropanol, n-butanol, tert-butanol, n-pentanol, tert-pentanol, sec-pentanol, n-hexanol, 2-hexanol, 3-hexanol, 2-ethylhexanol, 4-methyl-2-pentanol, n-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 3-methyl-3-heptanol, and 2-ethylhexanol.

[0023] Optionally, the metal of the metal ion includes at least one of Cu, Ag, Fe, Pb, Pt, Au, Sn, Ru, Rh, Co, Ce, Ti, Mo, and Zr.

[0024] Optionally, the metal ions are derived from metal compounds.

[0025] Optionally, the anion in the metal compound is at least one of sulfate, acetate, (hydrogen) phosphate and oxalate.

[0026] Optionally, the mass ratio of the alcohol compound to the metal compound is 10:1 to 1000:1.

[0027] Optionally, the upper limit of the mass ratio of the alcohol compound to the metal compound is selected from 15:1, 16:1, 20:1, 50:1, 100:1, 150:1, 200:1, 500:1 or 1000:1; the lower limit is selected from 10:1, 15:1, 16:1, 20:1, 50:1, 100:1, 150:1, 200:1 or 500:1.

[0028] Optionally, the added amount of the alcohol compound is 0.01% to 0.1% of the mass of 5-hydroxymethylfurfural.

[0029] Optionally, the amount of the alcohol compound added is such that the upper limit of the percentage of the mass of 5-hydroxymethylfurfural is selected from 0.05% or 0.1%; the lower limit is selected from 0.01% or 0.05%.

[0030] Optionally, the storage and transportation temperature range of the 5-hydroxymethylfurfural is -50 to 70°C.

[0031] Optionally, the pH value range of the 5-hydroxymethylfurfural is 5 to 8, and when the storage and transportation temperature range T is -50≤T≤10°C, the shelf life t of the 5-hydroxymethylfurfural is 24≤t≤36 months; when the storage and transportation temperature range is 10<T≤40°C, the shelf life t of the 5-hydroxymethylfurfural is 10≤t<24 months; when the storage and transportation temperature range is 40<T≤70°C, the shelf life t of the 5-hydroxymethylfurfural is 5≤t<10 months.

[0032] The light intensity involved in the storage and transportation of 5-hydroxymethylfurfural is 0-100000lx.

[0033] The 5-hydroxymethylfurfural involved in the storage and transportation process can be subjected to vortex, convection and horizontal oscillation stirring.

[0034] As one specific implementation method, the method described in the present application can extend the storage time of 5-hydroxymethylfurfural by at least 2.5 times compared to a solution without adding a reducing substance.

[0035] In the present application, "C1-C8" refers to the number of carbon atoms in the alcohol compound.

[0036] The storage and transportation described in this application include storage and transportation.

[0037] The beneficial effects of this application include:

[0038] (1) The present invention provides a new method for improving the stability of 5-hydroxymethylfurfural during storage and transportation;

[0039] (2) The content of reducing substances and metal ions added in the present invention is low, and the cost is low;

[0040] (3) The method provided by the present invention can significantly improve the stability of 5-hydroxymethylfurfural. DETAILED DESCRIPTION

[0041] The present application is described in detail below with reference to embodiments, but the present application is not limited to these embodiments.

[0042] In view of the fact that there is no dedicated solution to improve the stability of 5-hydroxymethylfurfural during storage and transportation, the inventors of this case have proposed the technical solution of the present invention after long-term research and extensive practice. The technical solution mainly utilizes the reducing properties of trace reducing compounds such as ferrous sulfate, sulfite and phenol compounds themselves, or forms a reducing environment with alcohol under the catalytic action of extremely trace metal ions such as Cu, Ag, Fe, Pb, Pt, Au, Sn, Ru, Rh, Co, Ce, Ti, Mo, Zr and other metal ions, eliminates free radical substances in the storage solution / solid of 5-hydroxymethylfurfural (HMF), prevents HMF from polymerization or decomposition and other side reactions, so as to improve the storage and transportation stability of HMF and extend the shelf life of HMF.

[0043] The technical solution of the present invention will be described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0044] Unless otherwise specified, the raw materials and catalysts in the examples of this application were purchased through commercial channels.

[0045] The measurement / calculation method of HMF purity and absorbance ratio in the present embodiment is the same as that in Example 1.

[0046] Example 1

[0047] 1 kg of 99.95% pure 5-hydroxymethylfurfural (HMF) was placed in a white plastic barrel, and its pH value was measured to be 8.0. 200 ppm of ferrous sulfate was added, and the mixture was sealed and placed in a 40°C constant temperature box. A small light was kept on in the incubator, and the light intensity in the barrel was measured by a illuminometer to be 10 lx. The barrel was placed for 10 months, and the HPLC (C 18Reverse phase chromatography column separation, UV detector 278nm wavelength detection, methanol and trifluoroacetic acid aqueous solution elution) analysis of HMF concentration, calculation of product purity, the longest time without change in HMF purity was 10.0 months, and the sample purity was 99.95%. Sample preparation method: accurately weigh 0.1g HMF and dissolve it in 1L deionized water to prepare a sample concentration of 0.1g / L. Analyze HMF concentration using high performance liquid chromatography using external standard method, the injection volume is 10μL, and the HMF sample purity calculation formula is as follows:

[0048]

[0049] During the preparation of HMF, colored impurities have strong absorption at 426nm. By measuring the absorbance value (OD 426nm ) changes to determine whether the sample has changed color, and the OD of the sample at a certain time t after storage and transportation 426nm t The OD of the sample at the initial time t0 426nm t0 Ratio OD 426nm t / OD 426nm t0 Indicates the magnitude of color change, and a value greater than 1.05 indicates significant color change. OD after 7.5 months 426nm t / OD 426nm t0 The ratio is 1.008, and the color change is not significant. After 10 months of storage, the purity of HMF is 99.89%, and the OD 426nm t / OD 426nm t0 The ratio is 1.022.

[0050] Example 2

[0051] 1kg of HMF with a purity of 99.97% was placed in a white plastic barrel, and its pH value was measured to be 5.2. 200ppm of ammonium bisulfite was added, mixed and sealed, and vortexed at 200rpm in a 50℃ constant temperature shaker. A small light was kept on in the shaker, and the light intensity in the barrel was measured by a illuminometer to be 25lx. After 10 months, the purity of HMF was tested every 15 days according to the method of Example 1. The longest time without change in HMF purity was 7 months, and the purity of the sample was 99.97%. OD 426nm t / OD 426nm t0 The ratio is 1.012.

[0052] Example 3

[0053] The HMF preservation method used in this example is the same as that in Example 2 except that the reducing agent is changed to 2,6-di-tert-butyl-p-cresol (BHT), the stirring mode is changed to 30 times / horizontal oscillation, the illumination intensity is changed to 10lx, and the temperature is changed to 50°C. The longest time for which the purity of HMF does not change is 8.0 months, and the purity of the sample is 99.97%. OD 426nm t / OD426nm t0 The ratio is 1.002.

[0054] Example 4

[0055] 1 kg of HMF with a purity of 99.98% was placed in a white plastic barrel, and its pH value was measured to be 6.0. 400 ppm of tert-butyl hydroquinone (TBHQ) was added, mixed and sealed, and stored in a 45°C constant temperature incubator. A small light was kept on in the incubator, and the light intensity in the barrel was measured by an illuminometer to be 10 lx. Other operations and detection methods were the same as those in Example 1. The longest time that the purity of HMF did not change was measured to be 9.5 months, and the purity of the HMF sample was 99.98%. OD 426nm t / OD 426nm t0 The ratio is 1.004.

[0056] Example 5

[0057] 1 kg of 5-hydroxymethylfurfural (HMF) with a purity of 99.98% was placed in a white plastic barrel, and its pH value was measured to be 6.0. 50 ppm of ferrous sulfate and 150 ppm of BHT were added, and after mixing, a 20 mL / s convection agitation was performed by a circulating pump, and the mixture was stored in a 45°C constant temperature box. The light intensity in the barrel was measured by an illuminometer to be 10 lx. Other operations and detection methods were the same as those in Example 1. The longest time that the purity of HMF did not change was measured to be 8.5 months, and the purity of the HMF sample was 99.98%. OD 426nm t / OD 426nm t0 The ratio is 1.005.

[0058] Example 6

[0059] The HMF preservation method used in this example is the same as that in Example 3 except that the amount of reducing agent BHT added is changed to 100 ppm, 100 ppm of sodium bisulfite is added, and stirring is not performed during the preservation process. The longest time for which the purity of HMF does not change is 9.0 months, and the purity of the HMF sample is 99.97%. OD 426nm t / OD 426nm t0 The ratio is 1.003.

[0060] Example 7

[0061] The HMF preservation method used in this example is the same as that in Example 1, except that the reducing agent is changed to 100 ppm potassium bisulfite and 100 ppm butylated hydroxyanisole (BHA), the stirring mode is vortex stirring at 200 rpm, the storage temperature is changed to 50°C, and the light intensity is changed to 25 lx. The other operations and detection methods are the same as those in Example 1. The longest time that the purity of HMF does not change is 8.0 months, and the purity of the HMF sample is 99.95%. OD 426nm t / OD 426nm t0The ratio is 1.008.

[0062] Table 1. Experimental data table of the longest shelf life of HMF in Examples 1 to 7

[0063]

[0064] Example 8

[0065] The HMF preservation method used in this example is the same as that in Example 1, except that the reducing agent is changed to 50 ppm sodium bisulfite, the stirring mode is 30 times / min horizontal oscillation, the preservation temperature is changed to 10°C, and the light intensity is changed to 10000 lx by using highly transparent glass and increasing the number of lamps. The longest time that the purity of HMF does not change is 24.0 months, and the purity of the HMF sample is 99.95%. OD 426nm t / OD 426nm t0 The ratio is 1.007.

[0066] Example 9

[0067] 1 kg of HMF with a purity of 99.97% was placed in a white plastic barrel, and its pH value was measured to be 5.2. 500 ppm of sodium bisulfite was added, and after mixing, it was placed in a -50°C ultra-low temperature refrigerator with a light intensity of 0 lx. Other operations and detection methods were the same as in Example 1. The longest time that the purity of HMF did not change was measured to be 36.0 months, and the purity of the HMF sample was 99.97%. OD 426nm t / OD 426nm t0 The ratio is 1.000.

[0068] Example 10

[0069] The HMF preservation method used in this example is the same as that in Example 4 except that the reducing agent is changed to 400 ppm BHT, the preservation temperature is changed to 15°C, and the light intensity is changed to 100 lx. The other operations and detection methods are the same as those in Example 4. The longest time for which the purity of HMF does not change is 19.5 months, and the purity of the HMF sample is 99.98%. OD 426nm t / OD 426nm t0 The ratio is 1.009.

[0070] Embodiment 11

[0071] 1 kg of HMF with a purity of 99.97% was placed in a glass jar, and its pH value was measured to be 5.2. 20 ppm of tert-butylhydroquinone (TBHQ) was added, and the mixture was placed in a 40°C constant temperature box, with a light intensity of 100,000 lx, no light at night, and a day-night cycle of 12:12. Other operations and detection methods were the same as those in Example 1. The longest time that the purity of HMF did not change was 10.0 months, and the purity of the HMF sample was 99.97%. OD 426nm t / OD 426nm t0 The ratio is 1.014.

[0072] Example 12

[0073] The HMF preservation method used in this example is the same as that in Example 10 except that the reducing agent is changed to 50ppm ferrous sulfate and 10ppm BHT, the preservation temperature is changed to 70°C, and the light intensity is changed to 10000lx. The other operations and detection methods are the same as those in Example 10. The longest time that the purity of HMF does not change is 5.0 months, and the purity of the HMF sample is 99.98%. OD 426nm t / OD 426nm t0 The ratio is 1.018.

[0074] Comparative Example 1

[0075] The HMF preservation method used in this example is the same as that in Example 12 except that no reducing agent is added. The longest time for which the purity of HMF does not change is 2.0 months, and the purity of the HMF sample is 99.98%. 426nm t / OD 426nm t0 The ratio is 1.019; after 5.0 months, the purity of the HMF sample becomes 90.21%, OD 426nm t / OD 426nm t0 The ratio is 1.063.

[0076] Embodiment 13

[0077] The HMF preservation method used in this example is the same as that in Example 9 except that the reducing agent is changed to 10 ppm sodium bisulfite and 10 ppm BHT. The longest time for which the purity of HMF does not change is 32.0 months, and the purity of the HMF sample is 99.97%. 426nm t / OD 426nm t0 The ratio is 1.002.

[0078] Table 2. Experimental data table of the longest shelf life of HMF in Examples 8 to 13 and Comparative Example 1

[0079]

[0080] Embodiment 14

[0081] The HMF preservation method used in this example is the same as that in Example 1 except that the reducing agent combination is changed to 1g methanol (0.1% of the mass of the HMF sample) and 0.1g titanium sulfate, and the light intensity is changed to 0lx. The other operations and detection methods are the same as those in Example 1. The longest time that the HMF purity does not change is 10.0 months, and the purity of the HMF sample is 99.95%. OD 426nm t / OD 426nm t0 The ratio is 1.003. When the storage time is 10.5 months, the purity of HMF sample is 99.93%, OD 426nm t / OD 426nm t0 The ratio is 1.008.

[0082] Embodiment 15

[0083] 1 kg of HMF with a purity of 99.98% was placed in a white plastic barrel, and its pH value was measured to be 6.0. A reducing agent combination of 1 g of methanol and 0.05 g of silver acetate was added, mixed and sealed, and stored in a 50°C constant temperature bath, and irradiated with outdoor sunlight in summer, with the light intensity set to 100000 lx. Other operations and detection methods were the same as in Example 1. The longest time that the purity of HMF did not change was measured to be 8.5 months, and the purity of the HMF sample was 99.98%. OD 426nm t / OD 426nm t0 The ratio is 1.015.

[0084] Example 16

[0085] The HMF preservation method used in this example is the same as that in Example 15, except that the reducing agent combination is changed to 0.5 g methanol (0.05% of the mass of the HMF sample) and 0.05 g stannous oxalate, the stirring method is changed to 60 times / horizontal oscillation, the preservation temperature is changed to 45°C, and the light intensity is set to 1000 lx. The longest time for which the HMF purity does not change is 8.0 months, and the purity of the HMF sample is 99.98%. OD 426nm t / OD 426nm t0 The ratio is 1.006.

[0086] Embodiment 17

[0087] 1 kg of HMF with a purity of 99.97% was placed in a white plastic barrel, and its pH value was measured to be 5.2. A reducing agent combination of 0.5 g isopropanol and 0.03 g titanium sulfate was added, mixed and sealed in a light-proof and stored in a 45°C constant temperature shaker, with the speed set to 200 rpm (vortex oscillation) and the light intensity set to 0 lx. Other operations and detection methods were the same as in Example 1. The longest time that the purity of HMF did not change was measured to be 9.0 months, and the purity of the HMF sample was 99.97%. OD 426nm t / OD426nm t0 The ratio is 1.004.

[0088] Embodiment 18

[0089] The HMF preservation method used in this example is the same as that in Example 15, except that the reducing agent combination is changed to 0.5 g n-butanol (0.05% of the HMF sample mass) and 0.05 g cobalt phosphate, the preservation temperature is changed to 60°C, and the light intensity is set to 10 lx. The other operations and detection methods are the same as those in Example 15. The longest time that the HMF purity does not change is 7.5 months, and the purity of the HMF sample is 99.98%. OD 426nm t / OD 426nm t0 The ratio is 1.008.

[0090] Embodiment 19

[0091] The HMF preservation method used in this example is the same as that in Example 17, except that the reducing agent combination is changed to 0.1 g 1-octanol (0.01% of the mass of the HMF sample) and 0.01 g cuprous acetate, the storage is left to stand, the storage temperature is changed to 70°C, and the light intensity is set to 100000 lx. The other operations and detection methods are the same as those in Example 17. The longest time that the HMF purity does not change is 5.0 months, and the purity of the HMF sample is 99.97%. OD 426nm t / OD 426nm t0 The ratio is 1.018.

[0092] Embodiment 20

[0093] The HMF preservation method used in this example is the same as that in Example 15, except that the reducing agent combination is changed to 1g 2-ethylhexanol and 0.001g stannous sulfate, and the light intensity is set to 0lx. The other operations and detection methods are the same as those in Example 15. The longest time that the HMF purity does not change is 9.0 months, and the purity of the HMF sample is 99.98%. OD 426nm t / OD 426nm t0 The ratio is 1.006.

[0094] Comparative Example 2

[0095] The HMF preservation method used in this example is the same as that in Example 20 except that the reducing agent combination is changed to only 0.001 g of stannous sulfate. The longest time for which the purity of HMF does not change is 4.5 months, and the purity of the HMF sample is 99.98%. 426nm t / OD 426nm t0 The ratio is 1.030.

[0096] Table 3. Experimental data table of the longest shelf life of HMF in Examples 14 to 20

[0097]

[0098] Embodiment 21

[0099] The HMF preservation method used in this example is the same as that in Example 15, except that the reducing agent combination is changed to 1g methanol and 0.1g titanium sulfate, the temperature is changed to -50°C, and the light intensity is set to 0lx. The longest time for which the HMF purity does not change is 36.0 months, and the purity of the HMF sample is 99.98%. OD 426nm t / OD 426nm t0 The ratio is 1.004.

[0100] Embodiment 22

[0101] The HMF preservation method used in this example is the same as that in Example 15, except that the reducing agent combination is changed to 1g methanol and 0.05g titanium sulfate, the temperature is changed to -20°C, and the stirring mode is changed to 60 times / min horizontal oscillation. The longest time that the HMF purity does not change is 30.5 months, and the purity of the HMF sample is 99.98%. OD 426nm t / OD 426nm t0 The ratio is 1.020.

[0102] Embodiment 23

[0103] The HMF preservation method used in this example is the same as that in Example 21 except that the temperature is changed to 10°C and the light intensity is set to 10000 lx. The other operations and detection methods are the same as those in Example 21. The longest time for which the purity of HMF does not change is 24.0 months, and the purity of the HMF sample is 99.98%. OD 426nm t / OD 426nm t0 The ratio is 1.006.

[0104] Embodiment 24

[0105] 1 kg of HMF with a purity of 99.98% was placed in a glass jar, and its pH value was measured to be 6.0. A reducing agent combination of 0.1 g isopropanol and 0.01 g cobalt phosphate was added, and the mixture was sealed after mixing. The mixture was stored in a 20°C constant temperature shaker, with the rotation speed set to 200 rpm (vortex type) and the light intensity set to 10000 lx. Other operations and detection methods were the same as those in Example 1. The longest time that the purity of HMF did not change was measured to be 15.0 months, and the purity of the HMF sample was 99.97%. OD 426nm t / OD 426nm t0 The ratio is 1.005.

[0106] Embodiment 25

[0107] The HMF preservation method used in this example is the same as that in Example 21, except that the reducing agent combination is changed to 0.1 g n-butanol and 0.01 g cobalt phosphate, the preservation temperature is changed to 50°C, and the light intensity is set to 10 lx. The other operations and detection methods are the same as those in Example 21. The longest time that the HMF purity does not change is 7.5 months, and the purity of the HMF sample is 99.98%. OD 426nm t / OD 426nm t0 The ratio is 1.008.

[0108] Embodiment 26

[0109] The HMF preservation method used in this example is the same as that in Example 21, except that the reducing agent combination is changed to 0.1 g 1-octanol and 0.001 g tin acetate, the preservation temperature is changed to 70°C, the light intensity is set to 100000 lx, and the stirring mode is changed to 60 times / min horizontal oscillation. The longest time that the purity of HMF does not change is 5.0 months, and the purity of the HMF sample is 99.98%. OD 426nm t / OD 426nm t0 The ratio is 1.023.

[0110] Embodiment 27

[0111] The HMF preservation method used in this example is the same as that in Example 21, except that the reducing agent combination is changed to 1g 2-ethylhexanol and 0.01g stannous oxalate, and the preservation temperature is changed to 40°C. The longest time for which the purity of HMF does not change is 10.0 months, and the purity of the HMF sample is 99.98%. OD 426nm t / OD 426nm t0 The ratio is 1.004.

[0112] Table 4. Experimental data table of the longest shelf life of HMF in Examples 21 to 27

[0113]

[0114] In addition, the inventors of this case also referred to the aforementioned embodiments and conducted experiments with other raw materials, process operations, and process conditions described in this specification, and obtained relatively ideal results.

[0115] The various aspects, embodiments, features and examples of the present invention should be considered as illustrative in all aspects and are not intended to limit the present invention, the scope of the present invention is defined only by the claims. Other embodiments, modifications and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.

[0116] The use of headings and sections in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the disclosure.

[0117] Throughout this disclosure, where a composition is described as having, containing, or comprising particular components, or where a process is described as having, containing, or comprising particular process steps, it is contemplated that the compositions taught by the present invention also consist essentially of or consist of the recited components, and that the processes taught by the present invention also consist essentially of or consist of the recited process steps.

[0118] It should be understood that the order of the various steps or the order in which a particular action is performed is not very important, as long as the teachings of the present invention remain operable. In addition, two or more steps or actions may be performed simultaneously.

[0119] Although the present invention has been described with reference to illustrative embodiments, it will be appreciated by those skilled in the art that various other changes, omissions and / or additions may be made without departing from the spirit and scope of the present invention and that the elements of the embodiments may be replaced by substantial equivalents. In addition, many modifications may be made without departing from the scope of the present invention to adapt specific circumstances or materials to the teachings of the present invention. Therefore, it is not intended herein to limit the present invention to the disclosed specific embodiments for performing the present invention, but it is intended that the present invention will include all embodiments within the scope of the appended claims. In addition, unless specifically stated, any use of the terms first, second, etc. does not indicate any order or importance, but rather uses the terms first, second, etc. to distinguish one element from another.

Claims

1. A method for improving the storage and transportation stability of 5-hydroxymethylfurfural, characterized in that: The method comprises: improving the storage and transportation stability of 5-hydroxymethylfurfural by using a reducing environment within a pH range of 5 to 8; Wherein, the reducing environment is: adding reducing substance B and trace metal ion compounds; The reducing substance B is at least one of C1 to C8 alcohols; The metal ion compound is at least one of titanium sulfate, silver acetate, stannous oxalate, cobalt phosphate, cuprous acetate, stannous sulfate and tin acetate.

2. The method according to claim 1, characterized in that The C1~C8 alcohol includes at least one of methanol, ethanol, propanol, isopropanol, n-butanol, tert-butanol, n-pentanol, tert-pentanol, sec-pentanol, n-hexanol, 2-hexanol, 3-hexanol, 2-ethylhexanol, 4-methyl-2-pentanol, n-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 3-methyl-3-heptanol, and 2-ethylhexanol.

3. The method according to claim 1, characterized in that The mass ratio of the alcohol to the metal ion compound is 10:1 to 1000:

1.

4. The method according to claim 1, characterized in that: The added amount of the alcohol is 0.01% to 0.1% of the mass of 5-hydroxymethylfurfural.

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