Method for preparing whole bio-based 2-nonanol by taking rhamnose waste liquid as raw material

Abstract

The invention discloses a method for preparing whole bio-based 2-nonanol by taking rhamnose waste liquid as a raw material, which comprises the following steps: taking the rhamnose waste liquid containing 3-hydroxydecanoic acid dimer and 3-hydroxydecanoic acid generated in the rhamnose production process as the raw material, taking water as a solvent, and reacting under the action of a catalyst and an additive under illumination to obtain the whole bio-based 2-nonanol. And reacting to obtain the whole bio-based 2-nonanol. The invention aims to prepare the whole bio-based 2-nonanol from the rhamnose waste liquid, on one hand, the oil phase waste liquid in the rhamnose production process can be recycled, the treatment cost of three wastes is reduced, and the added value of the product is increased, and on the other hand, the invention provides a novel method for preparing the whole bio-based 2-nonanol. The obtained whole bio-based 2-nonanol product better meets the requirements of people on safe, green and natural products at present.

Description

TECHNICAL FIELD

[0001] The present application relates to a new method for preparing full-biological 2-nonanol from rhamnose waste liquid. BACKGROUND

[0002] Rhamnose is a substance widely existing in polysaccharides, glycosides, vegetable gums and bacterial polysaccharides in plants, which can be used in food additives, health products, personal care and medicine, etc., and is an important chemical.

[0003] At present, rhamnose obtained by rhamnolipid hydrolysis is an important and feasible industrialization route, but due to the route, rhamnose is prepared by rhamnolipid hydrolysis, and an oil phase waste liquid is generated at the same time, which leads to poor atom economy, reduced economic value and decreased competitiveness. The rhamnose waste liquid generated by the rhamnolipid hydrolysis method generally contains a large amount of hydroxyalkyl acid, such as 3-hydroxydecanoic acid dimer and 3-hydroxydecanoic acid, and when it is treated as waste liquid, not only the waste liquid treatment cost needs to be increased, but also a large amount of resources is wasted. Therefore, it is of great significance to develop the reuse of rhamnose waste liquid.

[0004] 2-nonanol naturally exists in apples, bananas, strawberries and citrus fruits, and has wax, green, butter, orange, citrus and fruit fragrances. 2-nonanol is mainly used for blending cheese, mushroom, coconut, butter and other edible flavors, and the concentration in the final perfumed food is about 12-80 mg / kg. In addition to being used as a flavoring agent, it can also be used as a solvent and an organic synthesis intermediate, and has a wide range of applications. It is an important fine chemical.

[0005] At present, the synthesis methods of 2-nonanol mainly include: 1) 2-nonanol is synthesized by 2-nonanone, with a yield of about 98%; 2) 2-nonanol is synthesized by n-butyllithium and gamma-valerolactone, with a yield of about 76%. The current industrialization scheme has problems such as difficult source of reaction raw materials and harsh reaction conditions, and the obtained product is non-biological.

[0006] In summary, there are many shortcomings in the current industrialization route for synthesizing 2-nonanol, so it is of great significance to develop a new route to synthesize full-biological 2-nonanol with high yield and high selectivity. SUMMARY

[0007] The present application is different from the traditional synthesis method, and proposes a method for preparing full-biological 2-nonanol from rhamnose waste liquid. The present application aims to prepare full-biological 2-nonanol from rhamnose waste liquid, which can on the one hand reuse the oil phase waste liquid in the rhamnose production process, reduce the treatment cost of three wastes, increase the added value of products, and on the other hand provide a new method for preparing full-biological 2-nonanol, and the obtained full-biological 2-nonanol product is more in line with the current demand for safe, green and natural products.

[0008] To achieve the above object, the technical scheme adopted by the present application is as follows:

[0009] A method for preparing full-biological 2-nonanol from rhamnose waste liquid, comprising the following steps:

[0010] The rhamnose waste liquid produced in the rhamnose production process is used as raw material, water is used as solvent, and full-biological 2-nonanol is obtained through the action of catalyst and additive under illumination.

[0011] In the present application, the rhamnose waste liquid is mainly derived from the industrialized route of rhamnolipid hydrolysis to prepare rhamnose, which produces an oil phase waste liquid, which generally contains a large amount of hydroxyalkyl acid, such as 3-hydroxydecanoic acid dimer, 3-hydroxydecanoic acid, etc.

[0012] In the present application, as a typical component, the mass percentage composition of the rhamnose waste liquid includes: 3-hydroxydecanoic acid dimer 65-90%, 3-hydroxydecanoic acid 5-8%, 3-hydroxyoctanoic acid 1-7%, 3-hydroxydodecanoic acid 1-7%, and other components 3-13%.

[0013] In the method of the present application, the amount of water used is 1-20 times the mass of the rhamnose waste liquid, preferably 2-5 times.

[0014] In the method of the present application, the catalyst is selected from BiFeO3, SrTiO3, BiMnO3, BiCrO3, BiCoO3, NiFe2O4, ZnFe2O4, CaFe2O4, MgFe2O4, Ag3VO4, TiO2, Fe2O3, ZnS, CdS, WO3, etc., preferably BiFeO3;

[0015] In the method of the present application, the amount of catalyst used is 0.01-1 times the mass of the rhamnose waste liquid, preferably 0.05-0.1 times.

[0016] In the method of the present application, the additive is selected from LiCl, LiBF4, LiBr, LiPF6, KCl, KBr, NaCl, NaBr, CsCl, etc., preferably LiBF4;

[0017] In the method of the present application, the amount of additive used is 0.01-1 times the mass of the rhamnose waste liquid, preferably 0.05-0.1 times.

[0018] In the method of the present application, the illumination condition is to use LED lamps with a wavelength of 300-500 nm for irradiation, preferably LED lamps with a wavelength of 410 nm for irradiation.

[0019] In the method of the present invention, the reaction temperature is 20-100℃, the reaction time is 1-12h, preferably 60-80℃ for 2-5h.

[0020] Another object of the present invention is to provide a fully bio-based 2-nonanol.

[0021] A fully bio-based 2-nonanol was prepared using the above-described synthetic method for fully bio-based 2-nonanol.

[0022] The beneficial effects of this invention are as follows:

[0023] 1) The fully bio-based 2-nonanol is synthesized through photocatalytic reaction, and the raw material, rhamnose waste liquid, is derived from natural raw materials, making it fully bio-based, safer, greener, and meeting people's demand for natural products;

[0024] 2) The synthesis of fully bio-based 2-nonanol from rhamnose waste liquid not only solves the problem of waste liquid treatment, but also realizes waste utilization and increases the added value of rhamnose products. Detailed Implementation

[0025] The method of the present invention will be further illustrated below through specific embodiments, but the present invention is not limited to the listed embodiments, and should also include any other known modifications within the scope of the claims of the present invention.

[0026] Analytical instruments:

[0027] 1) Nuclear magnetic resonance spectrometer model: BRUKER ADVANCEⅢ400, 400MHz, CDCl3 as solvent;

[0028] 2) High-performance liquid chromatography (HPLC): Agilent Technologies 1200 series, equipped with a C18 HPLC column, column temperature set at 40℃, using acetonitrile and 0.03wt% phosphoric acid aqueous solution as the mobile phase, flow rate at 0.8 mL / min, detection at 285 nm wavelength using a UV detector, and quantification using the external standard method. Samples were appropriately diluted with acetonitrile before injection for analysis.

[0029] 3) Gas chromatograph: Agilent 7890, DB-5 separation column, vaporization chamber temperature 305℃, detector temperature 300℃, temperature ramping program: initial temperature 40℃, hold temperature for 10 min, ramp temperature to 130℃ at 5℃ / min, ramp temperature to 310℃ at 20℃ / min, hold temperature for 5 min.

[0030] Main raw material information:

[0031] Rhamnose oil phase waste liquid: prepared according to the method disclosed in patent CN112079709B;

[0032] BiFeO3, NiFe2O4, ZnFe2O4, Ag3VO4, TiO2, ZnS, particle size 40-60nm, chemical purity ≥98%, Alfaesa (China) Chemical Co., Ltd.

[0033] LiBF4, LiCl, LiPF6, KBr, CsCl, chemical purity ≥98%, Aladdin Biochemical Technology Co., Ltd.

[0034] Main synthesis equipment: LED photochemical reactor, three-necked glass flask.

[0035] Example 1

[0036] The oil phase waste liquid of rhamnose was analyzed and its mass percentage composition was as follows: 90% 3-hydroxydecanoic acid dimer, 5% 3-hydroxydecanoic acid, 1% 3-hydroxyoctanoic acid, 1% 3-hydroxydodecanoic acid, and 3% other components.

[0037] In a three-necked glass flask, 100g of rhamnose oil phase waste liquid, 10g of BiFeO3, 5g of LiBF4, and 200g of water were added sequentially at room temperature. The system was placed in an LED photochemical reactor, and stirring (300 rpm) and LED illumination (410 nm wavelength) were started. The temperature was programmed and increased until it reached 80°C. The reaction was continued for 2 hours, then stopped. The reaction solution was cooled to room temperature. Analysis by external standard liquid chromatography showed a 100% conversion rate of 3-hydroxydecanoic acid dimer and a 100% conversion rate of 3-hydroxydecanoic acid. Analysis by internal standard gas chromatography showed a 98% yield of 2-nonanol. The oil phase was separated from the reaction solution and washed with water. The washed oil phase was further purified by distillation under conditions of 36 trays, a reflux ratio of 5, a vacuum of 2 hPa, and a reboiler temperature of 160°C to obtain 2-nonanol. Product structure characterization: 1 H NMR (400MHz, CDCl3): δ3.75-3.82(m,1H),1.40-1.43(m,4H),1.29(brs,9H),1.19(dd,J=6.2,1.9Hz,3H),0.86-0.91(m,3H).

[0038] Example 2

[0039] The oil phase waste liquid of rhamnose was analyzed and its mass percentage composition was as follows: 82% 3-hydroxydecanoic acid dimer, 6% 3-hydroxydecanoic acid, 3% 3-hydroxyoctanoic acid, 3% 3-hydroxydodecanoic acid, and 6% other components.

[0040] In a three-necked glass flask, 100 g of rhamnose oil phase waste liquid, 5 g of NiFe₂O₄, 10 g of LiCl, and 500 g of water were added sequentially at room temperature. The system was placed in an LED photochemical reactor, and stirring (300 rpm) and LED illumination (405 nm wavelength) were started. The temperature was programmed and increased until it reached 60 °C. The reaction was continued for 5 hours, after which the reaction was stopped. The reaction solution was cooled to room temperature. Analysis by external standard liquid chromatography showed a 99% conversion rate of 3-hydroxydecanoic acid dimer and a 98% conversion rate of 3-hydroxydecanoic acid. Analysis by internal standard gas chromatography showed a 96% yield of 2-nonanol.

[0041] Example 3

[0042] The oil phase waste liquid of rhamnose was analyzed and its mass percentage composition was as follows: 76% 3-hydroxydecanoic acid dimer, 5% 3-hydroxydecanoic acid, 4% 3-hydroxyoctanoic acid, 4% 3-hydroxydodecanoic acid, and 11% other components.

[0043] In a three-necked glass flask, 100 g of rhamnose oil phase waste liquid, 50 g of ZnFe₂O₄, 50 g of LiPF₆, and 800 g of water were added sequentially at room temperature. The system was then placed in an LED photochemical reactor, with stirring (500 rpm) and LED illumination (420 nm wavelength) turned on. The reaction was carried out at 20°C for 1 hour, after which the reaction was stopped. The reaction solution was cooled to room temperature. Analysis by external standard liquid chromatography showed a 98% conversion rate of 3-hydroxydecanoic acid dimer and a 97% conversion rate of 3-hydroxydecanoic acid. Analysis by internal standard gas chromatography showed a 94% yield of 2-nonanol.

[0044] Example 4

[0045] The oil phase waste liquid of rhamnose was analyzed and its mass percentage composition was as follows: 65% 3-hydroxydecanoic acid dimer, 8% 3-hydroxydecanoic acid, 7% 3-hydroxyoctanoic acid, 7% 3-hydroxydodecanoic acid, and 13% other components.

[0046] In a three-necked glass flask, 100 g of rhamnose oil phase waste liquid, 10 g of Ag3VO4, 5 g of KBr, and 100 g of water were added sequentially at room temperature. The system was placed in an LED photochemical reactor, and stirring (300 rpm) and LED illumination (415 nm wavelength) were started. The temperature was programmed and increased until it reached 70°C. The reaction was continued for 3 hours, then stopped. The reaction solution was cooled to room temperature. Analysis by external standard liquid chromatography showed a 99% conversion rate of 3-hydroxydecanoic acid dimer and a 97% conversion rate of 3-hydroxydecanoic acid. Analysis by internal standard gas chromatography showed a 95% yield of 2-nonanol.

[0047] Example 5

[0048] The oil phase waste liquid of rhamnose was analyzed and its mass percentage composition was as follows: 65% 3-hydroxydecanoic acid dimer, 8% 3-hydroxydecanoic acid, 7% 3-hydroxyoctanoic acid, 7% 3-hydroxydodecanoic acid, and 13% other components.

[0049] In a three-necked glass flask, 100 g of rhamnose oil phase waste liquid, 1 g of TiO2, 100 g of CsCl, and 1000 g of water were added sequentially at room temperature. The system was then placed in an LED photochemical reactor, with stirring (600 rpm) and LED illumination (300 nm wavelength) activated. The temperature was programmed and increased until it reached 100 °C. The reaction was continued for 12 hours, after which the reaction was stopped. The reaction solution was cooled to room temperature. Analysis by external standard liquid chromatography showed a 96% conversion rate of 3-hydroxydecanoic acid dimer and a 96% conversion rate of 3-hydroxydecanoic acid. Analysis by internal standard gas chromatography showed a 91% yield of 2-nonanol.

[0050] Example 6

[0051] The oil phase waste liquid of rhamnose was analyzed and its mass percentage composition was as follows: 65% 3-hydroxydecanoic acid dimer, 8% 3-hydroxydecanoic acid, 7% 3-hydroxyoctanoic acid, 7% 3-hydroxydodecanoic acid, and 13% other components.

[0052] In a three-necked glass flask, 100 g of rhamnose oil phase waste liquid, 100 g of ZnS, 1 g of LiBF4, and 2000 g of water were added sequentially at room temperature. The system was then placed in an LED photochemical reactor, with stirring (600 rpm) and LED illumination (500 nm wavelength) activated. The temperature was programmed and increased until it reached 50 °C. The reaction was continued for 8 hours, after which it was stopped. The reaction solution was cooled to room temperature. Analysis by external standard liquid chromatography showed a 99% conversion rate of 3-hydroxydecanoic acid dimer and a 99% conversion rate of 3-hydroxydecanoic acid. Analysis by internal standard gas chromatography showed a 92% yield of 2-nonanol.

[0053] Comparative Example 1

[0054] The preparation method was the same as in Example 1, except that no additive LiBF4 was added, and other operations and conditions remained unchanged. The reaction solution was analyzed by liquid chromatography with external standard method, and the conversion rate of 3-hydroxydecanoic acid dimer was 38% and the conversion rate of 3-hydroxydecanoic acid was 36%. The reaction solution was analyzed by gas chromatography with internal standard method, and the yield of 2-nonanol was 12%.

Claims

1. A method for preparing fully bio-based 2-nonanol from rhamnose waste liquid, characterized in that, Includes the following steps: Using rhamnose waste liquid containing 3-hydroxydecanoic acid dimer and 3-hydroxydecanoic acid generated during the production process as raw material, and water as solvent, a fully bio-based 2-nonanol was obtained through the reaction under light irradiation with the action of catalysts and additives.

2. The method according to claim 1, characterized in that, The rhamnose waste liquid comprises, by mass percentage: 65-90% 3-hydroxydecanoic acid dimer, 5-8% 3-hydroxydecanoic acid, 1-7% 3-hydroxyoctanoic acid, 1-7% 3-hydroxydodecanoic acid, and 3-13% other components.

3. The method according to any one of claims 1-2, characterized in that, The amount of water used is 1-20 times the mass of the rhamnose waste liquid, preferably 2-5 times.

4. The method according to any one of claims 1-3, characterized in that, The catalyst is selected from at least one of BiFeO3, SrTiO3, BiMnO3, BiCrO3, BiCoO3, NiFe2O4, ZnFe2O4, CaFe2O4, MgFe2O4, Ag3VO4, TiO2, Fe2O3, ZnS, CdS, and WO3.

5. The method according to any one of claims 1-4, characterized in that, The amount of catalyst used is 0.01-1 times the mass of the rhamnose waste liquid, preferably 0.05-0.1 times.

6. The method according to any one of claims 1-5, characterized in that, The additive is selected from at least one of LiCl, LiBF4, LiBr, LiPF6, KCl, KBr, NaCl, NaBr, and CsCl.

7. The method according to any one of claims 1-6, characterized in that, The amount of the additive is 0.01-1 times the mass of the rhamnose waste liquid, preferably 0.05-0.1 times.

8. The method according to any one of claims 1-7, characterized in that, The lighting conditions are LED lights with a wavelength of 300-500nm.

9. The method according to any one of claims 1-8, characterized in that, The reaction temperature is 20-100℃, and the reaction time is 1-12h, preferably 60-80℃ for 2-5h.