Coffee grounds modified material, its preparation method and use

Abstract

The application discloses a coffee residue modified material and a preparation method and application thereof. The method comprises the following steps: adding coffee residue and nitrate into concentrated sulfuric acid, then adding potassium permanganate, stirring for at least 1 h, then adding hydrogen peroxide solution, heating to 90-98 DEG C, reacting for 1-5 h, then washing and filtering multiple times with dilute sulfuric acid, and then freeze-drying to obtain the coffee residue modified material. The modified material uses coffee residue as raw material, is environment-friendly, has mild preparation conditions, and is low in production cost; the modified material is used in the preparation of 3-hydroxypropane sulfonic acid, the product yield is high, sulfite does not need to be introduced to maintain pH, the content of by-product sulfite can be reduced, and the post-processing process and cost are reduced; in addition, the modified material is used as a catalyst, is conducive to recycling and application, has good application stability, and has a long service life.

Description

Technical Field

[0001] This invention relates to a modified material, and more particularly to a coffee grounds modified material, its preparation method, and its uses. Background Technology

[0002] The battery industry is currently experiencing rapid growth, and 1,3-propanesulfonate lactone is an important electrolyte additive, mainly used in power ternary batteries and digital batteries. Industrial preparation methods for 1,3-propanesulfonate lactone have been reported both domestically and internationally, all involving the initial preparation of the key intermediate 3-hydroxypropanesulfonic acid, followed by esterification to obtain 1,3-propanesulfonate lactone.

[0003] The current main method for synthesizing 3-hydroxypropanesulfonic acid is to use allyl alcohol and bisulfite as raw materials, adding a catalyst and reacting with the bisulfite to produce sodium 3-hydroxypropanesulfonate, which is then acidified. Chinese patent application number 201610591392.2 discloses a method using allyl alcohol and sodium bisulfite as reactants, with deionized water as the medium, at a reaction temperature of 30–80°C, and under the catalytic addition of an initiator aqueous solution to produce sodium 3-hydroxypropanesulfonate. The initiator is a mixture of sodium persulfate, hydrogen peroxide, and ferrous sulfate. The ferrous sulfate is used to adjust the pH of the system to neutral or weakly alkaline to maintain the stringent pH requirements of the reaction, but it causes the formation of sulfate byproducts, complicating post-processing. Furthermore, both methods involve the consumption of a single catalyst, which cannot be recycled, increasing production costs. Summary of the Invention

[0004] To address the aforementioned technical problems, this invention proposes a coffee grounds modified material, its preparation method, and its applications. The modified material uses coffee grounds as raw material, is environmentally friendly, requires mild preparation conditions, and has low production costs. When used in the preparation of 3-hydroxypropanesulfonic acid, the modified material yields a high product, eliminates the need for sulfite to maintain pH, reduces the content of byproduct sulfate, and lowers post-processing costs. Furthermore, using the modified material as a catalyst facilitates recycling, exhibits good recycling stability, and has a long catalyst lifespan.

[0005] This invention first provides a method for preparing a coffee grounds modified material, comprising the following steps: adding coffee grounds and nitrates to concentrated sulfuric acid, then adding potassium permanganate, stirring for at least 1 hour, adding hydrogen peroxide solution, heating to 90-98°C, reacting for 1-5 hours, washing and filtering multiple times with dilute sulfuric acid, and then drying to obtain the coffee grounds modified material.

[0006] This invention uses coffee grounds as raw material and, through multiple oxidation processes, produces a coffee grounds-modified catalyst that can be used in the catalytic reaction of 3-hydroxypropanesulfonic acid prepared from allyl alcohol and bisulfite. Coffee grounds are a biomass carbon material with a more porous network structure compared to activated carbon and other carbon materials. They possess not only a sponge-like morphology composed of macropores but also abundant micropores. Using coffee grounds as a matrix material for the above-mentioned modification can generate a sufficient number of peroxy groups. Further research has shown that the resulting catalyst can efficiently catalyze the synthesis of 3-hydroxypropanesulfonic acid without the addition of sulfite.

[0007] In this invention, the source of the coffee grounds is not limited; they can be any type of coffee beans that have been ground and used to extract water-soluble substances, leaving solid residue. More preferably, the coffee grounds contain 8-13% protein, 23-28% polysaccharides, and 1-2% fat by dry weight.

[0008] In a preferred embodiment of the preparation method of the present invention, the weight ratio of the nitrate to the coffee grounds is (1-2):1;

[0009] Preferably, the nitrate is selected from at least one of sodium nitrate, potassium nitrate, and calcium nitrate.

[0010] In a preferred embodiment of the preparation method of the present invention, the amount of concentrated sulfuric acid used is 40-50 times the mass of coffee grounds;

[0011] Preferably, the concentrated sulfuric acid has a mass concentration of 70-98 wt%.

[0012] In a preferred embodiment of the preparation method of the present invention, the amount of potassium permanganate added is 3-8 times the mass of the coffee grounds; and / or,

[0013] Adjust the system temperature to 35-40℃ before adding potassium permanganate; and / or,

[0014] After adding potassium permanganate, stir for 1-3 hours.

[0015] In a preferred embodiment of the preparation method of the present invention, the mass concentration of the hydrogen peroxide solution is 2-10 wt%; and / or,

[0016] The amount of hydrogen peroxide solution added is 80-120 times the mass of the coffee grounds.

[0017] In a preferred embodiment of the preparation method of the present invention, the mass concentration of the dilute sulfuric acid is 3-5 wt%; and / or,

[0018] The dilute sulfuric acid is used for washing at least three times;

[0019] Preferably, the drying method is freeze drying.

[0020] The present invention also provides a coffee grounds modified material prepared by the method described above.

[0021] This invention also provides the application of coffee grounds modified material prepared by the method described above in the catalytic preparation of 3-hydroxypropanesulfonic acid.

[0022] As a preferred embodiment of the present invention, the method includes the step of reacting dissolved allyl alcohol and bisulfite with coffee grounds modified material as catalyst to prepare 3-hydroxypropanesulfonate; after the reaction is completed, concentrated sulfuric acid is added to the filtrate for acidification to obtain 3-hydroxypropanesulfonic acid.

[0023] As a preferred embodiment in the application of the present invention, the reaction pressure is atmospheric pressure, the reaction temperature is 20-80℃, preferably 50℃-60℃, and the reaction time is 0.2-2h, preferably 0.8-1h;

[0024] Preferably, the mass concentration of the allyl alcohol in the solution system is 10-20 wt%, more preferably 12-18 wt%; and / or, the mass concentration of the bisulfite in the solution system is 18-36 wt%, more preferably 21-33 wt%.

[0025] The solubility system refers to a mixture of allyl alcohol, bisulfite and solvent, wherein the solvent is preferably water, or a mixture of water and other solvents.

[0026] Preferably, the bisulfite is selected from at least one of sodium bisulfite, potassium bisulfite, and calcium bisulfite;

[0027] Preferably, the amount of the coffee grounds modified material is 5-12 wt% of the mass of allyl alcohol;

[0028] Preferably, the amount of concentrated sulfuric acid used is 1.5-2 times the mass of allyl alcohol.

[0029] Furthermore, for the post-treatment method after acidification, any known purification method can be used to obtain the pure product, such as one or a combination of dehydration, extraction, vacuum distillation, and recrystallization.

[0030] The beneficial effects of this application are as follows:

[0031] A coffee grounds-modified catalyst with environmentally friendly, mild reaction conditions and simple process was prepared using coffee grounds as raw material. The synthesis of 3-hydroxypropanesulfonic acid using this catalyst avoids the use of sulfites, thereby reducing byproduct content and raw material consumption. Furthermore, it exhibits high catalytic efficiency, high product yield, and good stability for recycling, demonstrating significant application advantages. Detailed Implementation

[0032] The present invention will be further illustrated below with specific embodiments. These embodiments are merely illustrative and do not limit the scope of the invention.

[0033] Unless otherwise specified, all raw materials and reagents used in this invention can be purchased commercially. The coffee grounds used are those from Wanhua's own coffee grounds, which are solid residues produced after grinding Arabica beans. Analysis of their composition shows that they comprise 11% protein, 24% polysaccharides, and 1.8% fat by dry weight.

[0034] Examples 1-5 and Comparative Examples 1-3 are used to prepare different coffee grounds modified materials:

[0035] Example 1

[0036] Add 5g of coffee grounds and 5g of sodium nitrate to 230g of 98% concentrated sulfuric acid. Add 30g of potassium permanganate at 36℃ and stir for 1.5h. Then add 550g of 5% hydrogen peroxide aqueous solution and heat to 96℃. After reacting for 2h, wash 5 times with 4% sulfuric acid aqueous solution, filter, and freeze dry to obtain coffee grounds modified material A.

[0037] Example 2

[0038] Add 5g of coffee grounds and 10g of potassium nitrate to 200g of 98% concentrated sulfuric acid. Add 15g of potassium permanganate at 40℃ and stir for 2 hours. Then add 600g of 5% hydrogen peroxide aqueous solution and heat to 90℃. After reacting for 2 hours, wash 4 times with 4% sulfuric acid aqueous solution, filter, and freeze dry to obtain coffee grounds modified material B.

[0039] Example 3

[0040] Add 5g of coffee grounds and 8g of sodium nitrate to 250g of 98% concentrated sulfuric acid. Add 25g of potassium permanganate at 35°C and stir for 2 hours. Then add 400g of 8% hydrogen peroxide aqueous solution and heat to 98°C. After reacting for 2 hours, wash 8 times with 4% sulfuric acid aqueous solution, filter, and freeze dry to obtain coffee grounds modified material C.

[0041] Example 4

[0042] Add 5g of coffee grounds and 7g of sodium nitrate to 210g of 98% concentrated sulfuric acid. Add 40g of potassium permanganate at 38℃ and stir for 3h. Then add 500g of 5% hydrogen peroxide aqueous solution. Heat to 96℃ and react for 1.5h. Wash three times with 4% sulfuric acid aqueous solution, filter, and freeze dry to obtain coffee grounds modified material D.

[0043] Example 5

[0044] Add 5g of coffee grounds and 10g of sodium nitrate to 200g of 98% concentrated sulfuric acid. Add 35g of potassium permanganate at 36℃ and stir for 2 hours. Then add 550g of 2% hydrogen peroxide aqueous solution and heat to 95℃. After reacting for 4 hours, wash three times with 4% sulfuric acid aqueous solution, filter, and freeze dry to obtain coffee grounds modified material E.

[0045] Comparative Example 1

[0046] The coffee grounds modified material, denoted as F, was prepared using essentially the same method as in Example 1, except that the coffee grounds were replaced with activated carbon.

[0047] Comparative Example 2

[0048] The coffee grounds modified material, denoted as G, was prepared using essentially the same method as in Example 1, except that 98% concentrated sulfuric acid was replaced with water.

[0049] Comparative Example 3

[0050] The coffee grounds modified material, denoted as H, was prepared using essentially the same method as in Example 1, except that potassium permanganate and hydrogen peroxide were not added.

[0051] The following Examples 6-10 and Comparative Examples 4-7 prepared 3-hydroxypropanesulfonic acid using different methods:

[0052] Example 6

[0053] 100g of allyl alcohol, 180g of sodium bisulfite and 8g of coffee grounds modified material A were added to 700g of water and dispersed. The mixture was placed in a reaction vessel and reacted at 55℃ and normal pressure for 1 hour. After filtration, 170g of 98% concentrated sulfuric acid was added to the filtrate to obtain a solution of 3-hydroxypropanesulfonic acid.

[0054] Example 7

[0055] 88g of allyl alcohol, 165g of potassium bisulfite and 5g of coffee grounds modified material B were added to 420g of water and dispersed. The mixture was placed in a reaction vessel and reacted at 30°C and atmospheric pressure for 1 hour. After filtration, 170g of 98% concentrated sulfuric acid was added to the filtrate to obtain an aqueous solution of sodium 3-hydroxypropanesulfonate.

[0056] Example 8

[0057] 200g of allyl alcohol, 376g of calcium bisulfite and 5.5g of coffee grounds modified material C were added to 600g of water and dispersed. The mixture was placed in a reaction vessel and reacted at 60℃ and normal pressure for 1 hour. After filtration, 170g of 98% concentrated sulfuric acid was added to the filtrate to obtain an aqueous solution of sodium 3-hydroxypropanesulfonate.

[0058] Example 9

[0059] 100g of allyl alcohol, 188g of sodium bisulfite and 10g of coffee grounds modified material D were added to 500g of water and dispersed. The mixture was placed in a reaction vessel and reacted at 80℃ and normal pressure for 1 hour. After filtration, 170g of 98% concentrated sulfuric acid was added to the filtrate to obtain an aqueous solution of sodium 3-hydroxypropanesulfonate.

[0060] Example 10

[0061] 180g of allyl alcohol, 338g of sodium bisulfite and 12g of coffee grounds modified material E were added to 510g of water and dispersed. The mixture was placed in a reaction vessel and reacted at 60℃ and normal pressure for 1 hour. After filtration, 170g of 98% concentrated sulfuric acid was added to the filtrate to obtain an aqueous solution of sodium 3-hydroxypropanesulfonate.

[0062] Comparative Example 4

[0063] 3-hydroxypropanesulfonic acid was prepared using essentially the same method as in Example 6, except that coffee grounds modifier A was replaced with coffee grounds modifier F.

[0064] Comparative Example 5

[0065] 3-hydroxypropanesulfonic acid was prepared using essentially the same method as in Example 6, except that coffee grounds modifier A was replaced with coffee grounds modifier G.

[0066] Comparative Example 6

[0067] 3-hydroxypropanesulfonic acid was prepared using essentially the same method as in Example 6, except that coffee grounds modifier A was replaced with coffee grounds modifier H.

[0068] Comparative Example 7

[0069] 100g allyl alcohol, 180g sodium bisulfite, 20g sodium sulfite and 8g coffee grounds modified material A were added to 700g water and dispersed. The mixture was placed in a reaction vessel and reacted at 55℃ and normal pressure for 1 hour. After filtration, 170g of 98% concentrated sulfuric acid was added to the filtrate to obtain a solution of 3-hydroxypropanesulfonic acid.

[0070] The product yields (based on the molar yield of the raw material allyl alcohol) of the reaction schemes in Examples 6-10 and Comparative Examples 4-7 were tested, and the results are shown in Table 1. In addition, the modified coffee grounds obtained by filtration were repeated according to the methods in each example and comparative example, and the results are shown in Table 1.

[0071] Table 1. Performance Test Results

[0072]

[0073] The above description is only a preferred embodiment of the present invention. It should be noted that those skilled in the art can make several improvements and additions without departing from the method of the present invention, and these improvements and additions should also be considered within the scope of protection of the present invention.

Claims

1. The application of a coffee grounds-modified material in the catalytic preparation of 3-hydroxypropanesulfonic acid, characterized in that, The preparation method of the coffee grounds modified material includes the following steps: coffee grounds and nitrates are added to concentrated sulfuric acid, then potassium permanganate is added, and the mixture is stirred for at least 1 hour. Hydrogen peroxide solution is then added, the temperature is raised to 90-98°C, and the reaction is carried out for 1-5 hours. After washing and filtering with dilute sulfuric acid multiple times, the mixture is dried to obtain the coffee grounds modified material.

2. The application according to claim 1, characterized in that, The weight ratio of the nitrate to the coffee grounds is (1-2):

1.

3. The application according to claim 2, characterized in that, The nitrate is selected from at least one of sodium nitrate, potassium nitrate, and calcium nitrate.

4. The application according to claim 1, characterized in that, The amount of concentrated sulfuric acid used is 40-50 times the mass of the coffee grounds.

5. The application according to claim 4, characterized in that, The concentrated sulfuric acid has a mass concentration of 70-98 wt%.

6. The application according to any one of claims 1-5, characterized in that, The amount of potassium permanganate added is 3-8 times the mass of the coffee grounds; and / or, Adjust the system temperature to 35-40℃ before adding potassium permanganate; and / or, After adding potassium permanganate, stir for 1-3 hours.

7. The application according to any one of claims 1-5, characterized in that, The hydrogen peroxide solution has a mass concentration of 2-10 wt%; and / or, The amount of hydrogen peroxide solution added is 80-120 times the mass of the coffee grounds.

8. The application according to any one of claims 1-5, characterized in that, The mass concentration of the dilute sulfuric acid is 3-5 wt%; and / or, The dilute sulfuric acid is used for washing at least three times.

9. The application according to claim 8, characterized in that, The drying method is freeze drying.

10. The application according to any one of claims 1-5, characterized in that, The application method includes the steps of reacting dissolved allyl alcohol and bisulfite with coffee grounds modified material as catalyst to prepare 3-hydroxypropanesulfonate; after the reaction is completed, concentrated sulfuric acid is added to the filtrate for acidification to obtain 3-hydroxypropanesulfonic acid.

11. The application according to claim 10, characterized in that, The reaction pressure is atmospheric pressure, the reaction temperature is 20-80℃, and the reaction time is 0.2-2h.

12. The application according to claim 11, characterized in that, The reaction pressure is atmospheric pressure, the reaction temperature is 50℃-60℃, and the reaction time is 0.8-1h.

13. The application according to claim 11, characterized in that, The mass concentration of the allyl alcohol in the solution system is 10-20 wt%; and / or the mass concentration of the bisulfite in the solution system is 18-36 wt%.

14. The application according to claim 13, characterized in that, The allyl alcohol has a mass concentration of 12-18 wt% in the solution system; and / or the bisulfite has a mass concentration of 21-33 wt% in the solution system.

15. The application according to claim 11, characterized in that, The bisulfite is selected from at least one of sodium bisulfite, potassium bisulfite, and calcium bisulfite.

16. The application according to claim 11, characterized in that, The amount of coffee grounds modified material used is 5-12 wt% of the mass of allyl alcohol.

17. The application according to claim 11, characterized in that, The amount of concentrated sulfuric acid used is 1.5-2 times the mass of allyl alcohol.

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