Method for preparing high-purity melting rate regulator and plant essential oil from cornel seeds

Abstract

The present invention provides a method for preparing a high-purity melting rate regulator and plant essential oil from cornel seeds, belonging to the technical field of waste utilization. The method for preparing a high-purity melting rate regulator and plant essential oil from cornel seeds comprises the following steps: crushing cornel seeds to obtain cornel seed powder; mixing the cornel seed powder with a solvent for extraction to obtain cornel seed oil and defatted cornel seed powder; subjecting the defatted cornel seed powder to leaching to obtain cornel seed protein and filter residue; and subjecting the filter residue to high-temperature treatment to obtain cornel seed carbonaceous material. The present invention provides a comprehensive utilization method for cornel seeds to simultaneously obtain a high-purity melting rate regulator and plant essential oil, realizing the comprehensive and efficient utilization of cornel seeds.

Description

Technical Field

[0001] The present invention belongs to the technical field of waste utilization, and particularly relates to a method for preparing a high-purity melting rate regulator and plant essential oil from cornel kernels. Background Art

[0002] Continuous casting mold powder is an important metallurgical functional material in the steel production process, which is composed of a base material, a flux, and a carbonaceous melting rate regulator. The carbonaceous melting rate regulator can control the melting rate of the continuous casting mold powder. The melting rate determines the speed at which the continuous casting mold powder forms liquid slag, and is an important parameter for evaluating the ability of the continuous casting mold powder to supply liquid slag. The currently used melting rate regulators for continuous casting mold powder are mainly graphite, coke, carbon black, etc., and their sources are all non-renewable resources. With continuous consumption, these resources are becoming less and less, and the price is getting more and more expensive, and the restriction on the development of the mold powder will gradually become prominent. Therefore, it is of great significance to find a suitable substitute as the melting rate regulator.

[0003] Among many carbonaceous materials, in addition to graphite, carbon black, and coke from natural resources, there is also some wood charcoal from renewable resources, which is a dark brown or black porous solid fuel left after incomplete combustion of wood or woody raw materials, or pyrolysis under anaerobic conditions. Since wood is a renewable resource, the source of wood charcoal is more extensive than natural resources such as graphite, so it can be used as a new source of carbonaceous melting rate regulator for continuous casting mold powder.

[0004] Xixia County is the largest production base of continuous casting mold powder in China, and at the same time has the reputation of "the hometown of cornel", which is a special case in China and even the world. The cornel meat prepared from the skin of cornel is an important traditional Chinese medicine, while the medicinal value of the cornel kernels after peeling is relatively low, and they are generally stacked as waste materials and left to rot and weather naturally.

[0005] At present, the utilization of cornel seeds mainly focuses on the preparation of activated carbon. For example, the method for preparing activated carbon from cornel fruit seeds disclosed in patent document CN101966990A uses cornel fruit seeds as the raw material for manufacturing activated carbon. After the pretreated raw material and the activator are fully kneaded under stirring in an intermittent autoclave reactor treated with corrosion-resistant materials, carbon activation is carried out at a certain temperature to obtain an activated material, and then through processes such as recovering the activator, rinsing, dehydrating and drying, the finished activated carbon is prepared. Another example is the preparation method of cornel fruit seed activated carbon disclosed in patent document CN106395818A. This preparation method includes the following steps: (1) drying, crushing and sieving cornel fruit seeds; (2) adding a phosphoric acid activator to the sieved cornel fruit seed powder, performing ultrasonic treatment and standing for 12 hours; (3) filtering the treated liquid after standing and obtaining the residue; (4) carbonizing the residue on an electric furnace; (5) washing the carbonized residue with hydrochloric acid 4 times and rinsing with distilled water until the pH is 7; (6) drying, crushing and grinding the rinsed product to obtain the finished cornel fruit seed activated carbon.

[0006] In addition, there are also relevant studies on the extraction of cornel seed oil from cornel seeds. For example, the cornel seed oil extraction method disclosed in CN103614232A includes the following steps: 1) Preparation of materials: Select cornel seeds, sieve and pick out impurities, and rinse them clean with water; 2) Drying: Dry the rinsed cornel seeds to remove the surface moisture of the cornel seeds; 3) First denaturation: Keep the dried cornel seed husks at a temperature of 75°C - 85°C for 25s - 35s to denature the cornel seed husks and make the cornel seed meat cells expand rapidly; 4) Second denaturation: Immediately put the cornel seeds after the first denaturation into a container at -5°C - 10°C and stand for 8h - 12h to make the cornel seed meat cells shrink and denature; 5) Third denaturation: Heat the cornel seeds after the second denaturation to 85°C - 95°C and keep them warm for 15s - 20s to make the cornel seed meat cells expand rapidly for the second time; 6) Crushing: Crush the cornel seeds after the third denaturation into ultra-fine powder with a particle size of 0.5 - 100nm; 7) Fourth denaturation: Keep the crushed cornel seed micro-powder at 100°C - 150°C and a pressure of 0.2 - 0.4MPa for 50min - 70min to destroy the cornel seed meat cells; 8) Preliminary separation: Put the cornel seed micro-powder after the fourth denaturation into an ultrasonic container and use ultrasonic waves to destroy the cornel seed meat cell structure again to preliminarily separate the fatty acids and impurities in the micro-powder into a free state; 9) Pressing: Immediately send the cornel seed micro-powder after preliminary separation into a hot press to press and separate the cornel seed oil; 10) Ultrasonic impurity removal: Use ultrasonic waves to separate and remove impurities from the separated cornel seed oil; 11) Vacuum filtration: Perform vacuum filtration on the cornel seed oil obtained by ultrasonic impurity removal to obtain pure cornel seed oil.

[0007] The above studies do not involve the technology of using Cornus officinalis kernels in the preparation of carbonaceous melting rate regulators for continuous casting protection slag.

[0008] In view of this, the present invention is proposed. Summary of the invention

[0009] The technical problem to be solved by the present invention is to provide a comprehensive utilization method of cornus officinalis kernels in view of the deficiencies of the prior art, so as to simultaneously obtain a high-purity melting rate regulator and plant essential oil, thereby achieving comprehensive and efficient utilization of cornus officinalis kernels.

[0010] In order to solve the above technical problems, the technical solution adopted by the present invention is: a method for preparing a high-purity melting rate regulator and plant essential oil using cornus officinalis kernels, comprising the following steps:

[0011] S1: crushing cornus officinalis kernels to obtain cornus officinalis kernel powder;

[0012] S2: extracting the cornus officinalis kernel powder by mixing it with a solvent to obtain cornus officinalis kernel oil and defatted cornus officinalis kernel powder;

[0013] S3: extracting the defatted cornus officinalis kernel powder to obtain cornus officinalis kernel protein and filter residue;

[0014] S4: treating the filter residue at high temperature to obtain a Cornus officinalis core carbonaceous material.

[0015] The present invention takes the characteristics of cornus officinalis kernel into consideration as a whole, not only making the cornus officinalis kernel into a carbonaceous material that can be used as a melting rate regulator for continuous casting mold slag, but also reducing the content of elements such as phosphorus and sulfur in the cornus officinalis kernel that have an adverse effect on the mold slag as much as possible, so that the quality of the melting rate regulator is significantly improved. In this processing process, the cornus officinalis kernel not only does not waste raw materials due to the need to reduce elements such as phosphorus and sulfur, but also makes the raw materials more effectively and comprehensively developed, effectively extracts the cornus officinalis kernel oil and cornus officinalis kernel protein therein, realizes the comprehensive development and utilization of the cornus officinalis kernel, and has very high practical value.

[0016] In S1, the crushing is performed by using a crushing device commonly used in the technical field and currently sold on the market to crush the cornus kernels to a particle size of less than 5 mm.

[0017] Further, in S2, the solvent is at least one of n-hexane, petroleum ether, ethyl acetate and isopropanol.

[0018] Furthermore, in S2, the mixing ratio of the Cornus officinalis kernel powder and the solvent is 1 g: (10-25) ml.

[0019] Furthermore, in S2, the temperature of the mixed extraction is 60-100°C, the number of extractions is 2-5 times, and the extraction time is 2-6 hours.

[0020] Through the cooperation of the above processes and parameters, the essential oil components in the cornel seed powder can be effectively extracted and further utilized, and defatted cornel seed powder can be obtained simultaneously.

[0021] As a specific implementation of the present invention, S2: Weigh the cornel seed powder, add a solvent according to a solid-liquid ratio of 1:10 - 1:25 (g / ml), continuously extract 2 - 5 times at 60 - 100 °C, with an extraction time of 2 - 6 h, centrifuge, and remove the solvent in the supernatant with a rotary evaporator to obtain cornel seed oil. At the same time, dry the precipitate to obtain defatted cornel seed powder.

[0022] Furthermore, in S3, the extraction is carried out by using an alkali solution for extraction, followed by filtration to obtain a filtrate and a filter residue. The filtrate is adjusted to the isoelectric point with an acid solution and then centrifuged to obtain cornel seed protein. Among them, the determination of the isoelectric point is tested using a Zeta potential analyzer, and the isoelectric point is when the Zeta potential value is 0.

[0023] Furthermore, the alkali solution is at least one of sodium hydroxide solution, potassium hydroxide solution, magnesium hydroxide solution, and calcium hydroxide solution; the acid solution is at least one of hydrochloric acid, sulfuric acid, and nitric acid.

[0024] Furthermore, the concentration of the alkali solution is 1 - 3 mol / L, and the concentration of the acid solution is 1 - 3 mol / L.

[0025] Furthermore, the conditions for the extraction are a water bath at 40 - 60 °C, a continuous stirring time of 60 - 90 min, and the number of times is 1 - 2 times.

[0026] Through the cooperation of the above processes and parameters, the present invention can further extract the protein in the cornel seeds for full utilization.

[0027] As a specific implementation of the present invention, step S3: Adjust the defatted cornel seed powder to an alkaline state with a 1 - 3 mol / L alkali solution, continuously stir in a water bath at 40 - 60 °C for 60 - 90 min, centrifuge to obtain a filter residue and a filtrate; adjust the pH of the filtrate to the isoelectric point with a 1 - 3 mol / L acid solution and then centrifuge again to obtain cornel seed protein.

[0028] As a further preferred implementation of the present invention, step S3: Adjust the defatted cornel seed powder to an alkaline state with a 1 - 3 mol / L alkali solution, continuously stir in a water bath at 40 - 60 °C for 60 - 90 min, centrifuge to obtain a primary filter residue and a primary filtrate, subject the primary filter residue to secondary extraction to obtain a secondary filter residue and a secondary filtrate; combine the primary filtrate and the secondary filtrate, adjust the pH to the isoelectric point with a 1 - 3 mol / L acid solution and then centrifuge again to obtain cornel seed protein.

[0029] In the above steps, alkaline means pH > 7, preferably pH is 8.0 - 10.0.

[0030] Furthermore, S4 also includes washing and drying the filter residue.

[0031] Furthermore, the high-temperature treatment in S4 is to place the dried filter residue in a nitrogen furnace, first heat it from room temperature to 350 - 500 °C at a rate of 5 - 10 °C / min and hold for 1 - 2 h, then heat it to 600 - 800 °C at a rate of 5 - 10 °C / min and keep it warm for 1 - 3 h, and then cool it naturally to room temperature.

[0032] Furthermore, the mass content of C in the carbonaceous material of Cornus officinalis kernels is above 99.5%.

[0033] The present invention also provides the use of the carbonaceous material of Cornus officinalis kernels as a melting rate regulator for preparing continuous casting mold powder.

[0034] The application of the carbonaceous material of Cornus officinalis kernels in the present invention for preparing continuous casting mold powder, the continuous casting mold powder includes the carbonaceous material of Cornus officinalis kernels, and the addition amount of the carbonaceous material of Cornus officinalis kernels is 0.01% - 20% of the total weight of the continuous casting mold powder. On this basis, the addition amount of the carbonaceous material of Cornus officinalis kernels in the present invention can be adjusted conventionally according to the actual needs of different continuous casting mold powders, such as choosing to add 2%, 5%, 6%, 8%, 10%, 12%, 15%, 18% or 20%.

[0035] Cornus officinalis is the dried ripe flesh of Cornus officinalis Sieb. et Zucc. of the Cornaceae family, and has the effects of tonifying the liver and kidney, astringing essence and arresting seminal emission. Aliases: Shuzao (in "Shennong's Herbal Classic"), Shushi, Jizhu (in "Wu Pu's Herbal Classic"), Shanzhurou (in "Key to Therapeutics of Children's Diseases"), Shizao'er (in "Compendium of Materia Medica for Relief of Famine"), Rouzao (in "Compendium of Materia Medica"), Zaopi (in "Medical Compendium of Mirror of Agreement"), Yurou (in "Medical Compendium of Combining Chinese and Western Medicine"), Yaozao (in "Sichuan Traditional Chinese Medicine Annals"). Conventional processing methods are as follows: Shanzhurou: Remove impurities and remaining fruit kernels. Jiu Yuzhu: Take the clean Shanzhurou, mix it evenly with yellow rice wine, put it in a pot or other containers, seal it tightly, place it in a pot with water added, steam until the yellow rice wine is completely absorbed, and take it out to dry (20 catties of yellow rice wine are used for every 100 catties). Zheng Shanzhu: Put the picked and pitted Shanzhurou in a pot or steamer and other containers, seal it tightly, place it in a pot with water added, steam until it turns black on the outside, and take it out to dry. These processing methods all use the flesh of Cornus officinalis after removing the fruit kernels. The fruit kernels of Cornus officinalis are generally discarded and become agricultural and forestry waste.

[0036] Existing research has found that the organic chemical substances in fresh Cornus officinalis fruits mainly include reducing sugars, polysaccharides, organic acids, phenols, glycosides, iridoid glycosides, saponins, tannins, proteins, amino acids, vitamin B1, vitamin C, flavonoids, anthraquinones, steroids, triterpenes, lactones, coumarins, volatile oils, fatty acids, and trace elements, etc. Both the fruit pulp and the fruit pit contain more than a dozen amino acids, abundant vitamin B1, vitamin C, and more than 20 kinds of minerals. The fruit pit is also rich in nutrients, such as 4.61% protein, 8.56% fat, 20.33% sugar, 2.23% ash, and 51.62% crude fiber; 21 kinds of mineral elements, among which the content of phosphorus is higher than that of the fruit pulp, indicating that the fruit pit of Cornus officinalis also has the value of comprehensive utilization.

[0037] As a Chinese herbal medicine, Cornus officinalis contains many active ingredients, but different ingredients have different effects, and different extraction solvents, extraction methods, and different conditions are bound to cause differences in ingredients and contents. The extraction of monomers makes their efficacy, action intensity, etc. different, and the results are different, ultimately leading to differences in evaluation effects.

[0038] Currently, the main reported development and reuse of Cornus officinalis fruit pits mainly focus on the preparation of activated carbon, and there are also a small number of technical reports on the extraction of Cornus officinalis fruit pit oil.

[0039] On the one hand, in addition to the publicly reported literature listed in the background technology, there are other technical literatures on the method of preparing activated carbon from Cornus officinalis fruit pits that have not been elaborated in detail. The overall technological process mainly includes carbonization, activation, rinsing, and drying. Its preparation process aims to pursue a high specific surface area and high adsorption of activated carbon. Therefore, there are differences in technical problems and technical effects between preparing activated carbon from Cornus officinalis fruit pits and preparing a melting rate regulator for mold powder, and they have different technical concepts.

[0040] In addition, one of the main components of activated carbon is carbon element, but it has been verified that its use effect as a melting rate regulator for continuous casting mold powder is poor. On the one hand, it contains relatively high contents of impurity elements such as P and S that have an adverse impact on steel grades, and on the other hand, its carbon purity does not meet the usage requirements of the melting rate regulator. Therefore, it is impossible to obtain a high-purity carbonaceous material used as a melting rate regulator for continuous casting mold powder relying on the process of preparing activated carbon.

[0041] On the other hand, for the technical literature on preparing Cornus officinalis fruit pit oil from Cornus officinalis fruit pits, such as one of the publicly reported technologies CN103614232A listed in the background technology, it is to obtain pure Cornus officinalis fruit pit oil from Cornus officinalis fruit pits through material preparation, drying, primary denaturation, secondary denaturation, tertiary denaturation, crushing, quaternary denaturation, preliminary separation, pressing, ultrasonic impurity removal, and vacuum filtration. This process aims to obtain Cornus officinalis fruit pit oil as the only purpose, and the technological process is numerous and complex, which is different from the idea of comprehensive utilization of Cornus officinalis fruit pits.

[0042] The mold powder is an essential material in the current modern continuous casting process. This material plays a very important auxiliary role. The most critical technical parameters are mainly the melting point and the melting rate. Through these two parameters, the quality of the entire mold powder can be measured. Among them, the melting rate of the mold powder for continuous casting has an important impact on the thickness of the molten slag layer of the mold powder, the uniformity of the slag film, and the consumption of the mold powder. The melting rate regulator is one of the main components of the mold powder and is mainly used to adjust the melting rate of the mold powder. Currently, there is no relevant report on the preparation of a carbonaceous melting rate regulator for continuous casting mold powder using cornel seeds.

[0043] The existing carbonaceous melting rate regulators reported for continuous casting mold powder mainly include SiC, graphite, carbon black, etc., but they are expensive, limited in source, and non-renewable.

[0044] Cornel seeds contain a large amount of organic substances. The presence of these organic substances makes cornel seeds have certain utilization value. However, these organic substances contain relatively high amounts of P and S elements, up to 0.5 wt%. The large presence of these elements has an adverse impact on continuous casting of steel grades, which is significantly higher than the restrictive requirements of continuous casting mold powder.

[0045] At the same time, when directly carbonizing cornel seeds to prepare carbonaceous materials, the organic substances therein are wasted and not utilized.

[0046] Therefore, there is no existing technology for the comprehensive utilization of cornel seeds and their application to continuous casting mold powder. It is urgent to re-develop these waste resources, explore their potential utilization value, and promote the in-depth development of the cornel industry.

[0047] Compared with the existing technology, the beneficial effects of the present invention are as follows:

[0048] Based on the self-characteristics of cornel seeds and the related technology research on continuous casting mold powder, the present invention comprehensively extracts and utilizes cornel seeds. First, the cornel seeds are crushed to obtain cornel seed powder to improve the subsequent extraction efficiency; then the cornel seed powder is mixed with a solvent for extraction to obtain cornel seed oil and defatted cornel seed powder. This step uses solvent extraction, and the preferred solvent is at least one of n-hexane, petroleum ether, ethyl acetate, and isopropanol. Using the principle of similar solubility and optimizing the process parameters, specific essential oil components in cornel seeds are extracted; then the defatted cornel seed powder is leached to obtain cornel seed protein and filter residue. Specifically, it is leached with NaOH solution, filtered to obtain the filtrate and the filter residue, and the pH of the filtrate is adjusted to the isoelectric point with HCl and then centrifuged to effectively extract cornel seed protein through this process; finally, the filter residue is treated at high temperature to obtain cornel seed carbonaceous material.

[0049] It can be seen from this that the steps of the method of the present invention are connected before and after, closely combined, and support each other functionally and have an interaction relationship. As a whole, they jointly solve the comprehensive application of cornel seeds in the melting rate regulator for continuous casting powder and plant essential oil.

[0050] The C content in the carbonaceous material obtained by the method of the present invention is above 99.5 wt%, and the content of other impurity elements (specifically P element and S element) is less than 0.01 wt%. This is beneficial for preparing continuous casting powder with excellent performance and is expected to replace existing carbonaceous materials such as graphite, coke, and carbon black, so that the service performance of the continuous casting powder meets the industrial use requirements.

[0051] The present invention uses cornel seed carbonaceous material to prepare continuous casting powder, and it is confirmed that the cornel seed carbonaceous material plays a role in changing the melting point of the powder and regulating the melting speed of the powder. Moreover, when adding the cornel seed carbonaceous material prepared by the present invention to the continuous casting powder, the heat released during the oxidation process of the cornel seed carbonaceous material can make the carbonate in the continuous casting powder decompose more completely.

[0052] The purity of the cornel seed oil and cornel seed protein obtained by the method of the present invention is higher than 99.0%. The extraction rate of cornel oil is above 90%, and the extraction rate of cornel seed protein is above 80%. The two can be mixed and used as plant essential oil, and it is also convenient for other deep processing and reuse. BRIEF DESCRIPTION OF THE DRAWINGS

[0053] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for the description of the embodiments or the prior art. Obviously, the following drawings are only some embodiments of the present invention. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative efforts.

[0054] Figure 1 : Scanning electron microscope images of cornel seed carbonaceous material, where: a - Example 1, b - Example 2, c - Example 3, d - Example 4, e - Example 5;

[0055] Figure 2 : Carbonate decomposition performance curve graph. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0056] In order to better understand the present invention, the following further clearly elaborates the content of the present invention in combination with embodiments, but the protection scope of the present invention is not limited to the following embodiments. In the following description, a large number of specific details are given to provide a more thorough understanding of the present invention. However, it is obvious to those skilled in the art that the present invention can be implemented without one or more of these details.

[0057] In all the examples shown and discussed here, any specific values should be construed as merely exemplary and not as a limitation. Therefore, other examples of the exemplary embodiments may have different values.

[0058] Unless otherwise specified, all raw materials are sourced from commercially available products and, unless otherwise specified, do not contain other unspecified components except for inevitable impurities.

[0059] In the following examples, room temperature refers to a temperature of 25 ± 5°C.

[0060] Examples 1 - 5 are preparation examples of cornel seed carbonaceous materials.

[0061] Example 1

[0062] Provide cornel seeds, and crush the cleaned cornel seeds with a crusher;

[0063] Weigh cornel seed powder and place it in a Soxhlet extractor. Add n - hexane at a solid - liquid ratio of 1:10, and continuously extract at 60°C for 2 times, with each extraction time of 5 h. Centrifuge, and use a rotary evaporator to remove the solvent in the supernatant to obtain cornel seed oil. At the same time, dry the precipitate to obtain defatted cornel seed powder;

[0064] Adjust the defatted cornel seed powder to pH 10.0 with 1 mol / L NaOH solution, continuously stir in a water bath at 40°C for 90 min, then centrifuge and separate. The filter residue is subjected to secondary extraction. Adjust the pH of the filtrates obtained from the two extractions to the isoelectric point with 1 mol / L HCl and then centrifuge to obtain cornel seed protein;

[0065] Wash and dry the separated filter residue, place it in a nitrogen furnace, heat from room temperature to 380°C at a rate of 5°C / min and hold for 2 h, then heat to 650°C at a rate of 10°C / min and keep warm for 2.5 h, and then naturally cool to room temperature to obtain cornel seed carbonaceous material.

[0066] In this example, the mass content of C in the cornel seed carbonaceous material is 99.7%, and the contents of P and S elements are less than 0.005 wt%.

[0067] The purity of cornel seed oil is 99.1%, and the purity of cornel seed protein is 99.2%.

[0068] Example 2

[0069] Provide cornel seeds, and crush the cleaned cornel seeds with a crusher;

[0070] Weigh the cornel seed powder and place it in a Soxhlet extractor. Add n-hexane at a solid-liquid ratio of 1:15, and continuously extract twice at 70 °C, with each extraction time being 4 h. Centrifuge, and use a rotary evaporator to remove the solvent in the supernatant to obtain cornel seed oil. At the same time, dry the precipitate to obtain defatted cornel seed powder;

[0071] Adjust the defatted cornel seed powder to pH 9.5 with 2 mol / L KOH solution, continuously stir in a water bath at 45 °C for 85 min, then centrifuge and separate. The filter residue is subjected to secondary extraction. Adjust the pH of the filtrates obtained from the two extractions to the isoelectric point with 2 mol / L H 2 SO 4 solution and then centrifuge to obtain cornel seed protein;

[0072] Wash and dry the separated filter residue, place it in a nitrogen furnace, heat it from room temperature to 420 °C at a rate of 6 °C / min and hold for 2 h, then heat it to 600 °C at a rate of 8 °C / min and keep it for 3 h, and then naturally cool to room temperature to obtain cornel seed carbonaceous material.

[0073] In this example, the mass content of C in the cornel seed carbonaceous material is 99.6%, and the contents of P element and S element are less than 0.004 wt%.

[0074] The purity of cornel seed oil is 99.2%, and the purity of cornel seed protein is 99.2%.

[0075] Example 3

[0076] Provide cornel seeds, and crush the cleaned cornel seeds with a crusher;

[0077] Weigh the cornel seed powder and place it in a Soxhlet extractor. Add petroleum ether at a solid-liquid ratio of 1:18, and continuously extract three times at 80 °C, with each extraction time being 3 h. Centrifuge, and use a rotary evaporator to remove the solvent in the supernatant to obtain cornel seed oil. At the same time, dry the precipitate to obtain defatted cornel seed powder;

[0078] Adjust the defatted cornel seed powder to pH 9.0 with 2 mol / L Mg(OH) 2 solution, continuously stir in a water bath at 50 °C for 80 min, then centrifuge and separate. The filter residue is subjected to secondary extraction. Adjust the pH of the filtrates obtained from the two extractions to the isoelectric point with 2 mol / L HCl and then centrifuge to obtain cornel seed protein;

[0079] Wash and dry the separated filter residue, place it in a nitrogen furnace, heat it from room temperature to 350 °C at a rate of 7 °C / min and hold for 2 h, then heat it to 750 °C at a rate of 7 °C / min and keep it for 2 h, and then naturally cool to room temperature to obtain cornel seed carbonaceous material.

[0080] In this example, the mass content of C in the carbonaceous material of Cornus officinalis Sieb. et Zucc. kernels is 99.9%, and the contents of P element and S element are less than 0.005 wt%.

[0081] The purity of Cornus officinalis Sieb. et Zucc. kernel oil is 99.3%, and the purity of Cornus officinalis Sieb. et Zucc. kernel protein is 99.1%.

[0082] Example 4

[0083] Provide Cornus officinalis Sieb. et Zucc. kernels, and crush the cleaned Cornus officinalis Sieb. et Zucc. kernels with a crusher.

[0084] Weigh the Cornus officinalis Sieb. et Zucc. kernel powder and place it in a Soxhlet extractor. Add ethyl acetate at a solid-liquid ratio of 1:20, and continuously extract at 90 °C for 4 times, with each extraction time of 2 h. Centrifuge, and use a rotary evaporator to remove the solvent in the supernatant to obtain Cornus officinalis Sieb. et Zucc. kernel oil. At the same time, dry the precipitate to obtain defatted Cornus officinalis Sieb. et Zucc. kernel powder;

[0085] Adjust the defatted Cornus officinalis Sieb. et Zucc. kernel powder to pH 9.5 with 2 mol / L NaOH solution, and continuously stir in a water bath at 55 °C for 70 min. Then centrifuge and separate. The filter residue is subjected to secondary extraction. The filtrates obtained from the two extractions are adjusted to the isoelectric point with 3 mol / L HCl and then centrifuged to obtain Cornus officinalis Sieb. et Zucc. kernel protein;

[0086] Wash and dry the separated filter residue, place it in a nitrogen furnace, heat it from room temperature to 400 °C at a rate of 8 °C / min and hold for 1.5 h, then heat it to 700 °C at a rate of 6 °C / min and keep it warm for 1.5 h, and then naturally cool to room temperature to prepare the carbonaceous material of Cornus officinalis Sieb. et Zucc. kernels.

[0087] In this example, the mass content of C in the carbonaceous material of Cornus officinalis Sieb. et Zucc. kernels is 99.8%, and the contents of P element and S element are less than 0.006 wt%.

[0088] The purity of Cornus officinalis Sieb. et Zucc. kernel oil is 99.1%, and the purity of Cornus officinalis Sieb. et Zucc. kernel protein is 99.2%.

[0089] Example 5

[0090] Provide Cornus officinalis Sieb. et Zucc. kernels, and crush the cleaned Cornus officinalis Sieb. et Zucc. kernels with a crusher;

[0091] Weigh the Cornus officinalis Sieb. et Zucc. kernel powder and place it in a Soxhlet extractor. Add isopropanol at a solid-liquid ratio of 1:25, and continuously extract at 100 °C for 5 times, with each extraction time of 2 h. Centrifuge, and use a rotary evaporator to remove the solvent in the supernatant to obtain Cornus officinalis Sieb. et Zucc. kernel oil. At the same time, dry the precipitate to obtain defatted Cornus officinalis Sieb. et Zucc. kernel powder;

[0092] Adjust the defatted cornel seed powder to pH 9.0 with 3 mol / L NaOH solution, continuously stir it in a water bath at 60 °C for 60 min, then centrifuge and separate. The filter residue is subjected to secondary extraction. The filtrates obtained from the two extractions are adjusted to the isoelectric point with 3 mol / L HCl and then centrifuged to obtain cornel seed protein;

[0093] Wash and dry the separated filter residue, place it in a nitrogen furnace, heat it from room temperature to 500 °C at a rate of 10 °C / min and hold for 1 h, then heat it to 800 °C at a rate of 10 °C / min and keep it warm for 1 h, and then naturally cool it to room temperature to obtain cornel seed carbonaceous material.

[0094] In this example, the mass content of C in the cornel seed carbonaceous material is 99.9%, and the contents of P element and S element are less than 0.004 wt%.

[0095] The purity of cornel seed oil is 99.4%, and the purity of cornel seed protein is 99.2%.

[0096] Comparative Example 1

[0097] Provide cornel seeds, and crush the cleaned cornel seeds with a crusher; place the cornel seed powder in a nitrogen furnace, heat it from room temperature to 380 °C at a rate of 5 °C / min and hold for 2 h, then heat it to 650 °C at a rate of 10 °C / min and keep it warm for 2.5 h, and then naturally cool it to room temperature to obtain cornel seed carbonaceous material.

[0098] In this comparative example, the mass content of C in the cornel seed carbonaceous material is 97.6%, and the contents of P element and S element are 0.35 wt%.

[0099] Comparative Example 2

[0100] The difference between this Comparative Example 2 and Example 2 is as follows:

[0101] Weigh cornel seed powder and place it in a Soxhlet extractor, add ethanol at a solid-liquid ratio of 1:20, continuously extract it 3 times at 50 °C, with each extraction time of 5 h, centrifuge, and use a rotary evaporator to remove the solvent in the supernatant to obtain cornel seed oil. At the same time, dry the precipitate to obtain defatted cornel seed powder.

[0102] In this comparative example, the mass content of C in the cornel seed carbonaceous material is 98.3%, and the contents of P element and S element are less than 0.17 wt%.

[0103] The purity of cornel seed oil is 97.5%, and the purity of cornel seed protein is 98.6%.

[0104] Comparative Example 3

[0105] The difference between this Comparative Example 3 and Example 3 is as follows:

[0106] The separated filter residue was washed and dried, placed in a nitrogen furnace, heated from room temperature to 520 °C at a rate of 15 °C / min and held for 2 h, then heated to 850 °C at a rate of 20 °C / min and held for 2 h, and then naturally cooled to room temperature to obtain the cornel seed carbonaceous material.

[0107] In this comparative example, the mass content of C in the cornel seed carbonaceous material was 97.5%, and the contents of P and S elements were less than 0.01 wt%.

[0108] The following are the test examples of the cornel seed carbonaceous material.

[0109] 1. The cornel seed carbonaceous materials prepared in Examples 1 - 5 were scanned using a scanning electron microscope (SEM) to obtain SEM images.

[0110] Refer to Figure 1 , a shows that there are many large particles, the particle surface is relatively smooth, with distinct edges and corners, and there are no large amounts of small particles attached. b also has many large particles, but the number of small particles is relatively large, and some small particles are attached to the large particles. c shows that the particle size is relatively small, and many villi grow on the particle surface, which are actually a large number of small particles. d shows that the particles are relatively thin and there are a small number of small particles. e shows that the particles are relatively round and have no obvious edges and corners. It shows that the cornel seed carbonaceous material of the present invention has many changes in microscopic morphology, and different particle morphologies indicate different dispersion characteristics during its preparation process.

[0111] 2. The carbonate decomposition performance of the cornel seed carbonaceous material prepared by the present invention was tested, and the test method was as follows:

[0112] The experimental materials were mixed according to the weight ratio in Table 3. 1 g of the carbonate material was taken out and spread flat in a crucible, and the crucible was placed in a high-temperature furnace and heated at a constant rate of 10 °C / min to 400 °C. When the temperature reached 400 °C, 600 °C, 800 °C, and 1000 °C, the equipment was stopped, without heat preservation, and it was naturally cooled to room temperature. After it was naturally cooled to room temperature, the substances in the crucible were taken out, the mass of the carbonate material after the experiment was recorded and compared with that before the experiment, and the weight loss rate of the carbonate was calculated according to the above formula.

[0113] The weight loss rate can be calculated by the formula: Calculate.

[0114]

[0115] In the table: C0001 is the cornel seed carbonaceous material prepared in Example 1.

[0116] Result: Refer to Figure 2 , Curve 1 shows Na2 CO 3 has a relatively high decomposition temperature. Pure Na 2 CO 3 has a weight loss rate of 2%, which does not increase with the increase in temperature and will not decompose at 1000°C, so its weight loss rate remains unchanged. Curve 3 shows that the chemical reaction of the sample has been completely completed before 800°C. By comparing Curve 1 and Curve 3, it can be found that after adding the carbonaceous material of Cornus officinalis Sieb. et Zucc. kernels, the weight loss rate of the carbonate increases significantly because the carbonaceous material of Cornus officinalis Sieb. et Zucc. kernels reacts with air after heating, and the gaseous products after the reaction escape, increasing the weight loss of the carbonate.

[0117] Curve 2 shows that CaCO 3 starts to decompose below 600°C. When the temperature reaches about 800°C, the decomposition rate suddenly increases and is completely decomposed at 1000°C. At this time, the weight loss rate of CaCO 3 is 40%. Curve 4 shows that the chemical reaction of the sample has been completely completed before 400°C. By comparing Curve 2 and Curve 4, it can be found that after adding the carbonaceous material of Cornus officinalis Sieb. et Zucc. kernels, the weight loss rate of the carbonate increases significantly because the carbonaceous material of Cornus officinalis Sieb. et Zucc. kernels reacts with air after heating, and the gaseous products after the reaction escape and are not included in the mass of the carbonate after the experiment, increasing the weight loss of the carbonate.

[0118] When Curve 6 is compared with Curve 3, the weight loss rate of the carbonate decreases, and the weight loss rate coincides with the proportion of wollastonite added, indicating that wollastonite does not participate in the reaction in this experiment and has no effect on the decomposition of the carbonate.

[0119] When Curve 7 is compared with Curve 4, the weight loss rate of the carbonate decreases, and the weight loss rate coincides with the proportion of wollastonite added, indicating that wollastonite does not participate in the reaction in this experiment and has no effect on the decomposition of the carbonate.

[0120] In summary, when the carbonaceous material of Cornus officinalis Sieb. et Zucc. kernels prepared by the present invention is added to the continuous casting powder, the heat released during the oxidation process of the carbonaceous material of Cornus officinalis Sieb. et Zucc. kernels can make the carbonate in the continuous casting powder decompose more completely.

[0121] 3. The following are application examples and effects of the carbonaceous material of Cornus officinalis Sieb. et Zucc. kernels for preparing continuous casting powder.

[0122] Examples 6 - 10: Respectively provide 5 parts by weight of the carbonaceous material of Cornus officinalis Sieb. et Zucc. kernels prepared in Examples 1 - 5, 65 parts by weight of quartz, 15 parts by weight of calcite, 10 parts by weight of soda ash, and 5 parts by weight of fluorite. Mix the above raw materials, melt, cool and then grind to obtain the continuous casting powder.

[0123] Comparative Example 4: Provide 5 parts by weight of graphite, 65 parts by weight of quartz, 15 parts by weight of calcite, 10 parts by weight of soda ash, and 5 parts by weight of fluorite. Mix the above raw materials, melt, cool, and then grind to obtain a continuous casting mold powder.

[0124] Control Example: Provide 65 parts by weight of quartz, 15 parts by weight of calcite, 10 parts by weight of soda ash, and 5 parts by weight of fluorite. Mix the above raw materials, melt, cool, and then grind to obtain a continuous casting mold powder.

[0125] Measure the composition, melting point, and melting rate of the continuous casting mold powders obtained in Examples 6 - 10, Comparative Example 4, and the Control Example, where:

[0126] (1) Composition analysis: X-ray fluorescence spectrometer (XRF);

[0127] (2) Melting point and melting rate: Melting point and melting rate instrument;

[0128] The results are shown in the following table:

[0129] Composition (wt.%), melting point (°C), and melting rate (s) of the continuous casting mold powder

[0130]

[0131] As can be seen from the above table, when adding the cornel nucleus carbonaceous material of the present invention, the content of each component of the mold powder changes within a certain range, including fixed carbon, which indicates that the dispersion characteristics of the carbonaceous material in the mold powder will affect its distribution in the mold powder; at the same time, compared with Comparative Example 4, under the above changes, the cornel nucleus carbonaceous material of the present invention has the same effect as graphite and indeed plays a role in changing the melting point of the mold powder and regulating the melting rate of the mold powder in the mold powder; compared with the control example, the above regulation effect is significant.

[0132] In summary, the cornel nucleus carbonaceous material of the present invention can be used as a melting rate regulator for continuous casting mold powder and added to the continuous casting mold powder to regulate the melting rate and melting point of the mold powder.

[0133] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. Any other modifications or equivalent replacements made by those of ordinary skill in the art to the technical solutions of the present invention should be covered within the scope of the claims of the present invention as long as they do not depart from the spirit and scope of the technical solutions of the present invention.

Claims

1. Method for preparing high-purity melting rate regulator and plant essential oil from cornel seeds, Characterized in that: It includes the following steps: S1: Crush the cornel seeds to obtain cornel seed powder; S2: Mix and extract the cornel seed powder with a solvent, where the solvent is at least one of n-hexane, petroleum ether, ethyl acetate, and isopropyl alcohol, to obtain cornel seed oil and defatted cornel seed powder; S3: Leach the defatted cornel seed powder with an alkali solution, filter to obtain a filtrate and a filter residue; adjust the pH of the filtrate to the isoelectric point with an acid solution and then centrifuge to obtain cornel seed protein; S4: Wash the filter residue, dry it, place the dried filter residue in a nitrogen furnace, first heat it from room temperature to 350 - 500 °C at a rate of 5 - 10 °C / min and hold for 1 - 2 h, then heat it to 600 - 800 °C at a rate of 5 - 10 °C / min and keep it warm for 1 - 3 h, and naturally cool it to room temperature to obtain cornel seed carbonaceous material; Among them, the cornel seed carbonaceous material is used as a melting rate regulator for preparing continuous casting powder, and the cornel seed oil and the cornel seed protein are used as plant essential oils.

2. Method for preparing high-purity melting rate regulator and plant essential oil from cornel seeds according to claim 1, Characterized in that: The mixing ratio of the cornel seed powder to the solvent is 1 g : (10 - 25) ml.

3. Method for preparing high-purity melting rate regulator and plant essential oil from cornel seeds according to claim 2, Characterized in that: In S2, the temperature of the mixing extraction is 60 - 100 °C, the extraction times are 2 - 5 times, and the extraction time is 2 - 6 h.

4. Method for preparing high-purity melting rate regulator and plant essential oil from cornel seeds according to claim 3, Characterized in that: The alkali solution is at least one of sodium hydroxide solution, potassium hydroxide solution, magnesium hydroxide solution, and calcium hydroxide solution; the acid solution is at least one of hydrochloric acid, sulfuric acid, and nitric acid.

5. Method for preparing high-purity melting rate regulator and plant essential oil from cornel seeds according to claim 4, Characterized in that: The concentration of the alkali solution is 1 - 3 mol / L, and the concentration of the acid solution is 1 - 3 mol / L.

6. Method for preparing high-purity melting rate regulator and plant essential oil from cornel seeds according to claim 5, Characterized in that: The conditions for the leaching are a water bath at 40 - 60 °C, the continuous stirring time is 60 - 90 min, and the number of times is 1 - 2 times.

7. Melting rate regulator, made of cornel seed carbonaceous material prepared by the method according to any one of claims 1 - 6, where the mass content of carbon is above 99.5%.

8. Application of cornel seed carbonaceous material prepared by the method according to any one of claims 1 - 6 in continuous casting powder, and the addition amount of the cornel seed carbonaceous material is 0.01% - 20% of the total weight of the continuous casting powder.

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