Processing method of vegetable oil wax paste, method for producing vegetable oil and wax, their products and uses

Abstract

The present application provides a method for processing vegetable oil wax paste, comprising: treating the vegetable oil wax paste with an oxidant before extracting the vegetable oil wax paste with a solvent. The present application also provides a method for separating, extracting, enriching or producing vegetable oil or wax, and their products and uses.

Description

Technical Field

[0001] The present invention relates to the fields of chemistry and food, and in particular, to a method for processing vegetable oil wax paste, a method for producing vegetable oil and wax, and their products and uses. Background Art

[0002] Many oils obtained from plants in nature contain waxes, such as rice oil (rice bran oil), corn oil, sunflower oil, olive oil, etc. These waxes are mainly esters synthesized by plants during their growth. They are a mixture of esters composed of higher fatty acids and higher fatty alcohols. They coexist with oils in the cortex of plants and are separated from the oils during oil extraction or leaching. The presence of wax in oils affects their quality, and they are generally separated from oils by freezing. The separated by-product is called wax paste. The value of wax paste itself is very low, but after purification, it can be used in chemical, food and other industries, and has great economic value.

[0003] Taking rice bran oil (rice bran oil) as an example, rice bran oil wax paste (rice bran wax paste) is a byproduct in the rice bran oil refining process. The rice bran oil wax paste contains about 50% oil, and can be as high as 70%. Recycling the grease components in the wax paste can increase the yield of rice bran oil. In addition, the rice bran oil wax paste can be further processed into refined rice bran wax (wax) after de-oiling, thereby increasing the added value of the rice bran oil wax paste.

[0004] At present, solvent extraction is mainly used to extract grease from rice bran oil wax paste at home and abroad. Solvent extraction is to separate the neutral oil and wax in wax paste by using the difference in solubility of certain solvents and at a specific temperature. Table 6 shows the solubility, separability and filterability of rice bran wax in different solvents. Commonly used solvents include ethyl acetate, n-hexane, acetone, ethanol, etc. However, due to the problems of large solvent consumption, unsatisfactory separation effect, limited source and difficulty in recovery, it is still difficult to realize industrialization.

[0005] Table 6 Solubility, separation and filterability of rice bran wax in solvents

[0006]

[0007] At present, single solvents such as ethyl acetate, acetone, and isopropanol are mainly used to extract grease from rice bran oil wax paste. Although ethyl acetate is a solvent commonly used in industry for degreasing wax paste. However, according to the provisions of GB2760, ethyl acetate cannot be used as a processing aid for edible oils, so the grease extracted with ethyl acetate cannot be further processed into food-grade rice bran oil. Although acetone and short-chain alcohols such as isopropanol and ethanol can be used as processing aids, it is difficult to fully extract the grease in the wax paste due to poor solubility in grease. Considering the limitations of single solvents in performance, mixed solvents have also been reported. However, mixed solvents have poor stability, and the ratio between different solvents is difficult to ensure.

[0008] N-hexane (the main component of solvent No. 6) meets the relevant regulations for food processing aids. However, when using n-hexane as an extractant, rice bran wax is difficult to precipitate and separate under normal conditions, and the obtained oil has a high wax content, which cannot be achieved in industrial production. SUMMARY OF THE INVENTION

[0009] In a first aspect, the present application provides a method for processing vegetable oil wax paste, comprising:

[0010] Before the vegetable oil wax paste is extracted with a solvent, the vegetable oil wax paste is treated with an oxidizing agent.

[0011] In some embodiments of the processing method, the processing method further comprises:

[0012] performing solid-liquid separation after the extraction;

[0013] Optionally, the solvent is removed or recovered from the liquid phase to obtain the corresponding vegetable oil, and / or the solvent is removed or recovered from the solid phase to obtain the corresponding wax.

[0014] In a second aspect, the present application provides a method for separating, extracting, enriching or producing vegetable oil, comprising:

[0015] Treating vegetable oil wax paste with an oxidizing agent;

[0016] Using a solvent to extract the vegetable oil wax paste treated with an oxidant;

[0017] performing solid-liquid separation after the extraction;

[0018] The solvent is removed or recovered from the liquid phase to obtain the corresponding vegetable oil.

[0019] In a third aspect, the present application provides a method for separating, extracting, enriching or producing wax, comprising:

[0020] Treating vegetable oil wax paste with an oxidizing agent;

[0021] Using a solvent to extract the vegetable oil wax paste treated with an oxidant;

[0022] performing solid-liquid separation after the extraction;

[0023] The solvent is removed or recovered from the solid phase to obtain the corresponding wax.

[0024] In some embodiments of any of the foregoing aspects, the oxidant treatment is carried out at a temperature of not less than 60°C and not more than 100°C for a period of time; in some embodiments, the oxidant treatment is carried out under the following conditions: at a temperature of not less than 80°C, not less than 85°C, not less than 90°C, or not less than 95°C and not more than 100°C and / or a treatment time of not less than 10 min, not less than 30 min, not less than 1 h, not less than 1.5 h, or not less than 2 h.

[0025] In some embodiments of any of the foregoing aspects, the oxidant is selected from H2O2, potassium permanganate, sodium hypochlorite, perchloric acid, and combinations thereof, or solutions comprising them; in some embodiments, the solution is an aqueous solution; in some embodiments, the oxidant is selected from H2O2 and potassium permanganate, or solutions comprising them; in some embodiments, the oxidant is an aqueous solution of hydrogen peroxide with a mass concentration of 10%-50%, 15%-40%, 15%-35%, 20%-35% or 30%.

[0026] In some embodiments of any of the foregoing aspects, the oxidant is used in an amount of 1%-80%, 3%-65%, 5%-50%, 5%-45% or 10%-40% by weight of the rice bran oil wax paste to be treated.

[0027] In some embodiments of any of the foregoing aspects, the oxidant treatment step further comprises: allowing the mixture obtained after the oxidant treatment to stand and separate into layers, and taking the upper layer of wax paste for extraction.

[0028] In some embodiments of any of the foregoing aspects, the upper wax paste is dehydrated before extraction.

[0029] In some embodiments of any of the foregoing aspects, the dehydration treatment is vacuum drying.

[0030] In some embodiments of any of the foregoing aspects, the vacuum drying is performed at a temperature greater than 100°C.

[0031] In some embodiments of any of the foregoing, the method further comprises:

[0032] The vegetable oil wax paste subjected to the oxidant treatment step is mixed with the solvent for extraction.

[0033] In some embodiments of any of the foregoing aspects, the mixing ratio m:v of the vegetable oil wax paste subjected to the oxidant treatment step and the solvent is 1:1-1:20, 1:1-1:15, 1:1-1:10 or 1:1-1:5.

[0034] In some embodiments of any of the foregoing aspects, the vegetable oil wax paste is derived from a fat selected from the group consisting of rice bran oil, sunflower seed oil, palm oil, palm kernel oil, peanut oil, rapeseed oil, soybean oil, linseed oil, cottonseed oil, safflower seed oil, perilla seed oil, tea seed oil, castor seed oil, palm fruit oil, coconut oil, olive oil, cocoa bean oil, Chinese tallow seed oil, almond oil, apricot kernel oil, tung seed oil, rubber seed oil, corn oil, wheat germ oil, sesame seed oil, castor seed oil, linseed oil, evening primrose seed oil, hazelnut oil, pumpkin seed oil, walnut oil, grape seed oil, sesame seed oil, borage seed oil, sea buckthorn seed oil, tomato seed oil, macadamia nut oil, cocoa butter, algae oil, and combinations thereof.

[0035] In some embodiments of any of the foregoing aspects, the vegetable oil wax paste is selected from the group consisting of rice bran oil wax paste, sunflower seed oil wax paste, corn oil wax paste, and combinations thereof.

[0036] In some embodiments of any of the foregoing aspects, the solvent is n-hexane.

[0037] In some embodiments of any of the foregoing aspects, the extracting is performed under stirring.

[0038] In some embodiments of any of the foregoing aspects, the extraction is performed at a temperature of 20°C-69°C, 30°C-60°C, or 40°C-60°C.

[0039] In some embodiments of any of the foregoing aspects, the extraction time is 5 min-180 min, 10 min-150 min, 20 min-120 min, or 30 min-90 min.

[0040] In some embodiments of any of the foregoing aspects, before the solid-liquid separation step, the mixed liquid obtained after the extraction is cooled.

[0041] In some embodiments of any of the foregoing, the cooling temperature is -5°C-30°C, 0°C-30°C, 0°C-25°C, or 0°C-20°C.

[0042] In some embodiments of any of the foregoing aspects, the cooling time is no less than 0.5 h, no less than 1 h, no less than 1.5 h, or no less than 2 h.

[0043] In some embodiments of any of the foregoing aspects, the method of removing or recovering the solvent from the liquid phase is rotary evaporation.

[0044] In some embodiments of any of the foregoing aspects, the method of removing or recovering the solvent from the solid phase places the solid phase in an oven to remove or recover the solvent. In some embodiments, the oven is preferably an explosion-proof oven.

[0045] In some embodiments of any of the foregoing aspects, the solid-liquid separation is filtration; wherein the liquid phase is a filtrate and the solid phase is a filter cake.

[0046] In a fourth aspect, vegetable oil and / or wax are provided, which are obtained by the processing method of the vegetable oil wax paste described in the first aspect, the vegetable oil obtained by the method for separating, extracting, enriching or producing vegetable oil described in the second aspect, and the wax obtained by the method for separating, extracting, enriching or producing wax described in the third aspect.

[0047] In a fifth aspect, the present application provides food or food ingredients, which contain the vegetable oil or wax produced by the method described in the first, second or third aspect, or contain the vegetable oil or wax described in the fourth aspect or are prepared using the vegetable oil or wax described in the fourth aspect.

[0048] In a sixth aspect, the present application provides the use of an oxidant in increasing the recovery rate of fat in wax paste or reducing the wax content of fat recovered from wax paste or reducing the oil content of wax recovered from wax paste.

[0049] In some embodiments, the oxidant is selected from H2O2, potassium permanganate, sodium hypochlorite, perchloric acid and a combination thereof, or a solution containing them; for example, in certain embodiments, the solution is an aqueous solution; in yet other embodiments, the oxidant is selected from H2O2 and potassium permanganate, or a solution containing them; in yet other embodiments, the oxidant is an aqueous solution of hydrogen peroxide with a mass concentration of 10%-50%, 15%-40%, 15%-35%, 20%-35% or 30%.

[0050] In some embodiments, the wax paste is a vegetable oil wax paste, which is derived from the following oils and fats: rice bran oil, sunflower seed oil, palm oil, palm kernel oil, peanut oil, rapeseed oil, soybean oil, linseed oil, cottonseed oil, safflower seed oil, perilla seed oil, tea seed oil, castor seed oil, palm fruit oil, coconut oil, olive oil, cocoa bean oil, Chinese tallow seed oil, almond oil, apricot kernel oil, tung seed oil, rubber seed oil, corn oil, wheat germ oil, sesame seed oil, castor seed oil, linseed oil, evening primrose seed oil, hazelnut oil, pumpkin seed oil, walnut oil, grape seed oil, sesame seed oil, borage seed oil, sea buckthorn seed oil, tomato seed oil, macadamia oil, cocoa butter, algae oil and combinations thereof; for example, in certain embodiments, the vegetable oil wax paste is selected from rice bran oil wax paste, sunflower seed oil wax paste, corn oil wax paste and combinations thereof.

[0051] In some embodiments, the use comprises contacting the oxidant with the wax paste, and extracting the wax paste after contacting with the oxidant with a solvent to obtain the oil or the wax; for example, in some embodiments, the solvent is n-hexane.

[0052] Detailed Description of the Invention

[0053] definition

[0054] The following definitions are provided to better illustrate the content of this application and to guide ordinary technicians in the practice of the inventions of this application. Unless otherwise specified, the meanings of the terms in this application are the same as those generally understood by those skilled in the art.

[0055] As used herein, the terms "include" and "comprising" should be interpreted as inclusive and open-ended, rather than exclusive. Specifically, when used in the specification and claims, the terms "include" and "comprising" and their variations mean including the specified features, steps, or components. These terms should not be interpreted to exclude the presence of other features, steps, or components.

[0056] As used herein, the term "optional" or "optionally" means that the subsequently described event or circumstance can, but does not have to, occur, and the description includes instances where said event or circumstance occurs and instances where they do not occur.

[0057] Crude oil refers to primary oil obtained from animal or vegetable oils and has not been refined.

[0058] The source grease of crude oil comprises rice oil (rice bran oil), sunflower seed oil, palm oil, palm kernel oil, peanut oil, rapeseed oil, soybean oil, linseed oil, cottonseed oil, safflower seed oil, perilla seed oil, tea seed oil, castor oil, palm fruit oil, coconut oil, olive oil, cocoa bean oil, Chinese tallow seed oil, almond oil, apricot oil, tung oil, rubber seed oil, corn oil, wheat germ oil, sesame seed oil, castor oil, linseed oil, evening primrose seed oil, hazelnut oil, pumpkin seed oil, walnut oil, grape seed oil, sesame seed oil, borage seed oil, sea buckthorn seed oil, tomato seed oil, pumpkin seed oil, macadamia nut oil, coconut oil, cocoa butter, algae oil and / or their combination in any. Crude oil can be purchased commercially, or the oily material of plant origin can be squeezed or soaked by common means to obtain.

[0059] After these oils and fats are dewaxed, the composition containing a higher concentration of wax is the "vegetable oil wax paste" used in the present invention. The wax paste refers to a by-product produced during the refining process of edible oils and fats. The oils and fats from which the wax paste is derived include rice oil (or rice bran oil), sunflower oil, palm oil, palm kernel oil, peanut oil, rapeseed oil, soybean oil, linseed oil, cottonseed oil, safflower oil, perilla seed oil, tea seed oil, castor seed oil, palm fruit oil, coconut oil, olive oil, cocoa bean oil, Chinese tallow seed oil, almond oil, apricot kernel oil, tung oil, rubber seed oil, corn oil, wheat germ oil, sesame seed oil, castor seed oil, linseed oil, evening primrose seed oil, hazelnut oil, pumpkin seed oil, walnut oil, grape seed oil, sesame seed oil, borage seed oil, sea buckthorn seed oil, tomato seed oil, pumpkin seed oil, macadamia nut oil, coconut oil, cocoa butter, algae oil and / or any combination thereof.

[0060] The wax paste can be purchased from the market or prepared by conventional means, wherein examples of the wax paste include but are not limited to rice bran oil wax paste, sunflower seed oil wax paste, corn oil wax paste or a combination thereof.

[0061] Wherever a numerical range is given herein, that range includes its endpoints, and all individual integers and fractions within that range, and also includes each narrower range formed by all possible combinations of those endpoints and internal integers and fractions therein to form subgroups of the larger numerical group within that range to the same extent as if each of those narrower ranges were expressly stated. For example, the oxidant treatment is carried out at a temperature of not less than 60°C and not more than 100°C, that is, the temperature can be, for example, 60°C, 61°C, 62°C, 63°C, 64°C, 65°C, 66°C, 67°C, 68°C, 69°C, 70°C, 71°C, 72°C, 73°C, 74°C, 75°C, 76°C, 77°C, 78°C, 79°C, 80°C, 81°C, 82°C, 83°C, 84°C, 85°C, 86°C, 87°C, 88°C, 89°C, 90°C, 91°C, 92°C, 93°C, 94°C, 95°C, 96°C, 97°C, 98°C, 99°C or 100°C, etc. and ranges formed by them. Specific implementation plan

[0062] In a first aspect, the present application provides a method for processing vegetable oil wax paste, comprising:

[0063] Before the vegetable oil wax paste is extracted with a solvent, the vegetable oil wax paste is treated with an oxidizing agent.

[0064] In some embodiments of the processing method, the processing method further comprises:

[0065] performing solid-liquid separation after the extraction;

[0066] Optionally, the solvent is removed or recovered from the liquid phase to obtain the corresponding vegetable oil, and / or the solvent is removed or recovered from the solid phase to obtain the corresponding wax.

[0067] In a second aspect, the present application provides a method for separating, extracting, enriching or producing vegetable oil, comprising:

[0068] Treating vegetable oil wax paste with an oxidizing agent;

[0069] Using a solvent to extract the vegetable oil wax paste treated with an oxidant;

[0070] performing solid-liquid separation after the extraction;

[0071] The solvent is removed or recovered from the liquid phase to obtain the corresponding vegetable oil.

[0072] In a third aspect, the present application provides a method for separating, extracting, enriching or producing wax, comprising:

[0073] Treating vegetable oil wax paste with an oxidizing agent;

[0074] Using a solvent to extract the vegetable oil wax paste treated with an oxidant;

[0075] performing solid-liquid separation after the extraction;

[0076] The solvent is removed or recovered from the solid phase to obtain the corresponding wax.

[0077] In some embodiments of any of the foregoing aspects, the oxidant treatment is at a temperature of not less than 60°C and not more than 100°C (e.g., 60°C, 61°C, 62°C, 63°C, 64°C, 65°C, 66°C, 67°C, 68°C, 69°C, 70°C, 71°C, 72°C, 73°C, 74°C, 75°C, 76°C, 77°C, 78°C, 79°C, 80°C, 81°C, 82°C, 83°C, 84°C, 85°C, 86°C, 87°C, 88°C, 89°C, 90°C, 91°C, 92°C, 93°C, 94°C, 95°C, 96°C, 97°C, 98°C, 99°C or 100°C, etc.) for a period of time. In some embodiments, the oxidant treatment is carried out under the following conditions: at a temperature of not less than 80°C, not less than 85°C, not less than 90°C, or not less than 95°C and not more than 100°C and / or a treatment time of not less than 10 min (e.g., not less than 10 min, not less than 20 min, not less than 30 min, not less than 40 min, not less than 50 min, not less than 1 h, not less than 1.2 h, not less than 1.5 h, not less than 1.8 h, not less than 2 h, not less than 2.5 h, not less than 3 h, not less than 3.8 h, not less than 4 h, not less than 4.5 h, not less than 4.8 h or not less than 5 h), not less than 30 min, not less than 1 h, not less than 1.5 h, or not less than 2 h.

[0078] In some embodiments of any of the foregoing aspects, the oxidant is selected from H2O2, potassium permanganate, sodium hypochlorite, perchloric acid, and combinations thereof, or solutions comprising them; in some embodiments, the solution is an aqueous solution; in some embodiments, the oxidant is selected from H2O2 and potassium permanganate, or solutions comprising them; in some embodiments, the oxidant is an aqueous solution of hydrogen peroxide with a mass concentration of 10%-50% (e.g., 10%, 12%, 15%, 20%, 22%, 24%, , 27%, 30%, 32%, 35%, 38%, 40%, 42%, 45%, 48% or 50%, etc.), 15%-40%, 15%-35%, 20%-35% or 30%.

[0079] In some embodiments of any of the foregoing aspects, the oxidant is used in an amount of 1%-80% (e.g., 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39% by weight) of the vegetable oil wax paste to be treated. %, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79% or 80%, etc.), 3%-65%, 5%-50%, 5%-45% or 10%-40%. For example, the oxidant is a hydrogen peroxide aqueous solution with a mass concentration of 30% and the amount of the hydrogen peroxide aqueous solution is not less than 20% of the weight of the vegetable oil wax paste to be treated.

[0080] In some embodiments of any of the foregoing aspects, the oxidant treatment step further comprises: allowing the mixture obtained after the oxidant treatment to stand and separate into layers, and taking the upper layer of wax paste for extraction.

[0081] In some embodiments of any of the foregoing aspects, the upper wax paste is dehydrated before extraction.

[0082] In some embodiments of any of the foregoing aspects, the dehydration treatment includes but is not limited to vacuum drying.

[0083] In some embodiments of any of the foregoing aspects, the vacuum drying is carried out at a temperature greater than 100°C (e.g., 101°C, 102°C, 103°C, 104°C, 105°C, 106°C, 107°C, 108°C, 109°C, 110°C, 111°C, 112°C, 113°C, 114°C, 115°C, 116°C, 117°C, 118°C, 119°C, 120°C, 125°C, 130°C, 137°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, etc., e.g., 101°C-120°C). In some embodiments of any of the foregoing aspects, the method further comprises:

[0084] The vegetable oil wax paste subjected to the oxidant treatment step is mixed with the solvent for extraction.

[0085] In some embodiments of any of the foregoing aspects, the mixing ratio m:v of the vegetable oil wax paste undergoing the oxidant treatment step and the solvent is 1:1-1:20 (e.g., 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19 or 1:20, etc.), 1:1-1:15, 1:1-1:10 or 1:1-1:5.

[0086] In some embodiments of any of the foregoing aspects, the vegetable oil wax paste is derived from a fat selected from the group consisting of rice bran oil, sunflower seed oil, palm oil, palm kernel oil, peanut oil, rapeseed oil, soybean oil, linseed oil, cottonseed oil, safflower seed oil, perilla seed oil, tea seed oil, castor seed oil, palm fruit oil, coconut oil, olive oil, cocoa bean oil, Chinese tallow seed oil, almond oil, apricot kernel oil, tung seed oil, rubber seed oil, corn oil, wheat germ oil, sesame seed oil, castor seed oil, linseed oil, evening primrose seed oil, hazelnut oil, pumpkin seed oil, walnut oil, grape seed oil, sesame seed oil, borage seed oil, sea buckthorn seed oil, tomato seed oil, macadamia nut oil, cocoa butter, algae oil, and combinations thereof.

[0087] In some embodiments of any of the foregoing aspects, the vegetable oil wax paste is selected from the group consisting of rice bran oil wax paste, sunflower seed oil wax paste, corn oil wax paste, and combinations thereof.

[0088] In some embodiments of any of the foregoing aspects, the solvent is n-hexane.

[0089] In some embodiments of any of the foregoing aspects, the extracting is performed under stirring.

[0090] In some embodiments of any of the foregoing aspects, the extraction is carried out at a temperature of 20°C-69°C (e.g., 20°C, 21°C, 22°C, 23°C, 24°C, 25°C, 26°C, 27°C, 28°C, 29°C, 30°C, 31°C, 32°C, 33°C, 34°C, 35°C, 36°C, 37°C, 38°C, 39°C, 40°C, 41°C, 42°C, 43°C, 44°C, 45°C, 46°C, 47°C, 48°C, 49°C, 50°C, 51°C, 52°C, 53°C, 54°C, 55°C, 56°C, 57°C, 58°C, 59°C, 60°C, 61°C, 62°C, 63°C, 64°C, 65°C, 66°C, 67°C, 68°C, or 69°C, etc.), 30°C-60°C, or 40°C-60°C.

[0091] In some embodiments of any of the foregoing aspects, the extraction time is 5 min-180 min (e.g., 5 min, 10 min, 15 min, 20 min, 25 min, 30 min, 35 min, 40 min, 45 min, 50 min, 55 min, 60 min, 65 min, 70 min, 75 min, 80 min, 90 min, 95 min, 100 min, 105 min, 110 min, 115 min, 120 min, 125 min, 130 min, 135 min, 140 min, 145 min, 150 min, 155 min, 160 min, 165 min, 170 min, 175 min, or 180 min, etc.), 10 min-150 min, 20 min-120 min, or 30 min-90 min.

[0092] In some embodiments of any of the foregoing aspects, before the solid-liquid separation step, the mixed liquid obtained after the extraction is cooled.

[0093] In some embodiments of any of the foregoing, the cooling temperature is -5°C-30°C (e.g., -5°C, -4°C, -3°C, -2°C, -1°C, 0°C, 1°C, 2°C, 3°C, 4°C, 5°C, 6°C, 7°C, 8°C, 9°C, 10°C, 11°C, 12°C, 13°C, 14°C, 15°C, 16°C, 17°C, 18°C, 19°C, 20°C, 21°C, 22°C, 23°C, 24°C, 25°C, 26°C, 27°C, 28°C, 29°C, or 30°C, etc.), 0°C-30°C, 0°C-25°C, or 0°C-20°C.

[0094] In some embodiments of any of the foregoing aspects, the cooling time is not less than 0.5 h (e.g., not less than 0.5 h, not less than 1 h, not less than 1.2 h, not less than 1.5 h, not less than 1.8 h, not less than 2 h, not less than 3 h, or not less than 4 h, etc.) or not less than 2 h.

[0095] In some embodiments of any of the foregoing aspects, the method of removing or recovering the solvent from the liquid phase is rotary evaporation.

[0096] In some embodiments of any of the foregoing aspects, the method of removing or recovering the solvent from the solid phase places the solid phase in an oven to remove or recover the solvent. In some embodiments, the oven is an explosion-proof oven.

[0097] In some embodiments of any of the foregoing aspects, the solid-liquid separation is filtration; wherein the liquid phase is a filtrate and the solid phase is a filter cake.

[0098] In a fourth aspect, the present application provides vegetable oils and / or waxes obtained by the processing method of the vegetable oil wax paste described in the present disclosure, vegetable oils obtained by the method for separating, extracting, enriching or producing vegetable oils described in the present disclosure, and waxes obtained by the method for separating, extracting, enriching or producing waxes described in the present disclosure.

[0099] In a fifth aspect, the present application provides food or food ingredients, which contain vegetable oil or wax produced by the method described in the first, second or third aspect, or contain the vegetable oil or wax described in the fourth aspect or are prepared using the vegetable oil or wax described in the fourth aspect. The food can be, for example, edible oil, blended oil, products that require edible oil in the production process, etc.

[0100] In a sixth aspect, the present application provides the use of an oxidant in increasing the recovery rate of fat in wax paste or reducing the wax content of fat recovered from wax paste or reducing the oil content of wax recovered from wax paste.

[0101] The present invention provides a method for extracting oil and wax from vegetable oil wax paste. The wax and the mixed oil are separated by an extraction separation method after oxidant treatment, and then the solvent in the mixed oil is separated to obtain the oil. The inventions of this application provide one or more of the following advantages:

[0102] The mixed solution obtained after extraction is easier to separate solid from liquid. For example, the filtration speed is fast during filtration separation, and the filter cake does not stick to the filter cloth, which is convenient for separation and can be industrialized.

[0103] The extracted oil has a low wax content, for example, less than 5% in some cases, and can be further processed into food-grade vegetable oil or directly used in food and edible oil to increase the yield of vegetable oil. At the same time, the wax obtained has a low oil content, light color and high purity.

[0104] Example

[0105] The following examples are for illustration purposes only and are not intended to limit the scope of this application.

[0106] Comparative Example 1:

[0107] Acetone extraction: Take a certain amount of rice bran oil wax paste and acetone at a ratio of 1:3 (m:v) at room temperature and pressure, and stir and extract for 1 hour. Weigh 400g of the mixture of wax paste and solvent and introduce it into a Buchner funnel for vacuum filtration, and record the filtration time. After the filtration is completed, observe the state of the filtrate and filter cake. After removing the acetone from the filtrate, calculate the rice bran oil recovery rate and wax content. After removing the acetone from the filter cake, calculate the purity of bran wax.

[0108] Comparative Example 2

[0109] Ethyl acetate extraction: Take a certain amount of rice bran oil wax paste and mix it with ethyl acetate in a ratio of 1:3 (m:v), stir and extract at 75℃ for 1h, cool to 20℃, and cool for 2h. Weigh 400g of the mixture of wax paste and solvent and introduce it into a Buchner funnel for vacuum filtration, and record the filtration time. After the filtration, observe the state of the filtrate and filter cake. After removing the ethyl acetate from the filtrate, calculate the rice bran oil recovery rate and wax content. After removing the ethyl acetate from the filter cake, calculate the purity of bran wax.

[0110] Comparative Example 3

[0111] Isopropanol extraction: Take a certain amount of rice bran oil wax paste and mix it with isopropanol in a ratio of 1:3 (m:v), stir and extract at 79°C for 1h, cool to 20°C, and cool for 2h. Weigh 400g of the mixture of wax paste and solvent and introduce it into a Buchner funnel for vacuum filtration, and record the filtration time. After the filtration, observe the state of the filtrate and filter cake. After removing the isopropanol in the filtrate, calculate the rice bran oil recovery rate and wax content. After removing the isopropanol in the filter cake, calculate the purity of bran wax.

[0112] Comparative Example 4:

[0113] Normal temperature extraction with n-hexane: Take a certain amount of rice bran oil wax paste and mix it with n-hexane at a ratio of 1:5 (m:v) at room temperature and pressure, and stir and extract for 1 hour. Weigh 400g of the mixture of wax paste and solvent and introduce it into a Buchner funnel for vacuum filtration, and record the filtration time. After the filtration is completed, observe the state of the filtrate and filter cake. After removing the acetone from the filtrate, calculate the rice bran oil recovery rate and wax content. After removing the acetone from the filter cake, calculate the purity of the bran wax.

[0114] Comparative Example 5:

[0115] High-temperature extraction with n-hexane: Mix a certain amount of rice bran oil wax paste with n-hexane in a ratio of 1:5 (m:v), stir and extract at 60°C for 1h, cool to 0°C, and cool for 2h. Weigh 400g of the mixture of wax paste and solvent and introduce it into a Buchner funnel for vacuum filtration, and record the filtration time. After the filtration, observe the state of the filtrate and filter cake. After removing the n-hexane from the filtrate, calculate the recovery rate of rice bran oil and the wax content. After removing the n-hexane from the filter cake, calculate the purity of bran wax.

[0116] Embodiment 1:

[0117] Extraction after hydrogen peroxide treatment:

[0118] 1. Heat the rice bran oil wax paste to 85°C, add 5% of the weight of the wax paste in a hydrogen peroxide solution (concentration 30%), react at 8°C for 1 hour, and after the reaction is completed, keep the temperature and stand for stratification. After stratification, take the upper wax paste, heat it to 105°C, vacuum dry and dehydrate it, and obtain the rice bran oil wax paste.

[0119] 2. Extraction: Take a certain amount of the rice bran oil wax paste obtained in step 1 and mix it with normal hexane in a ratio of 1:5 (m:v), stir and extract at 60°C for 1h, cool at 0°C, and cool for 2h. Weigh 400g of the mixture of wax paste and solvent and introduce it into a Buchner funnel for vacuum filtration, and record the filtration time. After the filtration, observe the state of the filtrate and the filter cake. After removing the normal hexane in the filtrate, calculate the recovery rate of rice bran oil and the wax content. After removing the normal hexane in the filter cake, calculate the purity of bran wax.

[0120] Embodiment 2:

[0121] Extraction after hydrogen peroxide treatment:

[0122] 1. Heat the rice bran oil wax paste to 85°C, add 10% of the weight of the wax paste in a hydrogen peroxide solution (concentration 30%), react at 85°C for 1 hour, and after the reaction is completed, keep the temperature and stand for stratification. After stratification, take the upper wax paste, heat it to 105°C, vacuum dry and dehydrate it, and obtain the rice bran oil wax paste.

[0123] 2. Extraction: Take a certain amount of the rice bran oil wax paste obtained in step 1 and mix it with normal hexane in a ratio of 1:5 (m:v), stir and extract at 60°C for 1h, cool at 0°C, and cool for 2h. Weigh 400g of the mixture of wax paste and solvent and introduce it into a Buchner funnel for vacuum filtration, and record the filtration time. After the filtration, observe the state of the filtrate and the filter cake. After removing the normal hexane in the filtrate, calculate the recovery rate of rice bran oil and the wax content. After removing the normal hexane in the filter cake, calculate the purity of bran wax.

[0124] Embodiment 3:

[0125] Extraction after hydrogen peroxide treatment:

[0126] 1. Heat the rice bran oil wax paste to 95°C, add 20% of the weight of the wax paste in a hydrogen peroxide solution (concentration 30%), react at 95°C for 2h, and after the reaction is completed, keep warm and stand for stratification. After stratification, take the upper wax paste, heat to 105°C, vacuum dry and dehydrate to obtain rice bran oil wax paste.

[0127] 2. Extraction: Take a certain amount of the rice bran oil wax paste obtained in step 1 and mix it with normal hexane in a ratio of 1:5 (m:v), stir and extract at 60°C for 1h, cool at 0°C, and cool for 2h. Weigh 400g of the mixture of wax paste and solvent and introduce it into a Buchner funnel for vacuum filtration, and record the filtration time. After the filtration, observe the state of the filtrate and the filter cake. After removing the normal hexane in the filtrate, calculate the recovery rate of rice bran oil and the wax content. After removing the normal hexane in the filter cake, calculate the purity of bran wax.

[0128] Embodiment 4-12

[0129] Examples 4-12 were experimented in a similar manner to Examples 1 to 3, but the experimental conditions were as shown in Table 3 below, and the results of Examples 4-12 are shown in Table 3.

[0130] Detection Methods

[0131] 2.1 Method for determining the separation effect of mixed liquid:

[0132] After the extraction, weigh 400g of the mixture of solvent and bran wax, and filter it with a filter cloth with a diameter of 9cm. The vacuum degree is controlled at 500mbar. The timing starts from the moment the mixture is introduced into the funnel and ends when no clear liquid flows out of the filtration bottle. Record the filtration time. After the filtration, take out the filter cloth and observe the state of the filter cake on the filter cloth to see if it is sticky and whether it is easy to separate and fall off.

[0133] 2.2 Rice bran wax oil content detection method:

[0134] Weigh a certain amount of rice bran wax (m1) in a 100 mL centrifuge tube, add acetone to dissolve, and centrifuge (speed 8000g, time 15min). After separation, pour out the supernatant and add acetone again to wash until the supernatant is colorless. Pour out the supernatant and put the centrifuge tube in an oven to dry the solvent.

[0135]

[0136] 2.3 Wax content detection method in oil:

[0137] Filter the rice bran oil when it is heated to 100°C. Weigh a certain amount of oil sample after filtration at room temperature, add 5 times the amount of water-saturated butanone solution, stir and dissolve thoroughly, let stand for 10 minutes, slowly pour the solution into a quantitative filter paper of known mass M2 (the filter paper has been placed in a Gooch funnel) and filter (electric filtration or power filtration), and repeatedly wash with water-saturated butanone solution until it is colorless. Place the quantitative filter paper in a 105°C oven for 1 hour, weigh M1, and then bake for 40 minutes and weigh until constant weight.

[0138] The wax content is calculated as follows:

[0139] W=(M1-M2) / m

[0140] Where: W: mass fraction of wax;

[0141] M1: mass of quantitative filter paper containing sediment, g;

[0142] M2: mass of quantitative filter paper, g;

[0143] m: sample mass, g;

[0144] The experimental results of the comparative examples and embodiments are shown in Tables 1 to 3 below, respectively.

[0145] Table 1

[0146]

[0147] Table 2

[0148]

[0149]

[0150] The solvent wax paste mixed liquid obtained by the method of the present invention has a fast filtering speed, the filter cake does not stick to the filter cloth, is easy to separate, and can be industrially produced. The extracted oil has a low wax content and can be further processed into food-grade vegetable oil to increase the yield of vegetable oil. At the same time, the wax obtained has a low oil content and high purity.

[0151] The exemplary embodiments of the various inventions of the present application are described above; however, without departing from the essence and scope of the present application, those skilled in the art will be able to modify or improve the exemplary embodiments described in the present application, and the resulting variations or equivalents also fall within the scope of the present application.

Claims

1. A method for processing vegetable oil wax paste, comprising: Before extracting the vegetable oil wax paste with a solvent, treating the vegetable oil wax paste with an oxidant; The oxidant treatment is carried out at a temperature of not less than 60°C and not more than 100°C for a period of 1 h to 5 h; The amount of the oxidant is 5%-80% of the weight of the vegetable oil wax paste to be treated; The solvent is n-hexane.

2. The method of claim 1, further comprising: The extraction is followed by solid-liquid separation.

3. The method of claim 2, further comprising removing or recovering the solvent from the liquid phase to obtain the corresponding vegetable oil, and / or removing or recovering the solvent from the solid phase to obtain the corresponding wax.

4. Methods for separating, extracting, enriching or producing vegetable oils, comprising: Treating vegetable oil wax paste with an oxidizing agent; Using a solvent to extract the vegetable oil wax paste treated with an oxidant; performing solid-liquid separation after the extraction; removing or recovering the solvent from the liquid phase to obtain the corresponding vegetable oil; The oxidant treatment is carried out at a temperature of not less than 60°C and not more than 100°C for a period of 1 h to 5 h; The amount of the oxidant is 5%-80% of the weight of the vegetable oil wax paste to be treated; The solvent is n-hexane.

5. Methods for separating, extracting, enriching or producing waxes, including: Treating vegetable oil wax paste with an oxidizing agent; Using a solvent to extract the vegetable oil wax paste treated with an oxidant; performing solid-liquid separation after the extraction; Removing or recovering the solvent from the solid phase to obtain the corresponding wax; The oxidant treatment is carried out at a temperature of not less than 60°C and not more than 100°C for a period of 1 h to 5 h; The amount of the oxidant is 5%-80% of the weight of the vegetable oil wax paste to be treated; The solvent is n-hexane.

6. The method according to any one of claims 1 to 5, wherein: The oxidant treatment is performed at a temperature of not less than 80°C and not more than 100°C.

7. The method according to any one of claims 1 to 5, wherein: The oxidant treatment is performed at a temperature of not less than 85°C and not more than 100°C.

8. The method according to any one of claims 1 to 5, wherein: The oxidant treatment is performed at a temperature of not less than 90°C and not more than 100°C.

9. The method according to any one of claims 1 to 5, wherein: The oxidant treatment is performed at a temperature of not less than 95°C and not more than 100°C.

10. The method according to any one of claims 1 to 5, wherein: The oxidant treatment is carried out for a period of not less than 1.5 h to 5 h.

11. The method according to any one of claims 1 to 5, wherein: The oxidant treatment is carried out for a period of not less than 2 h to 5 h.

12. The method of any one of claims 1 to 5, wherein the oxidizing agent is selected from H2O2, potassium permanganate, sodium hypochlorite, perchloric acid and combinations thereof, or solutions containing the same.

13. The method of claim 12, wherein the solution is an aqueous solution.

14. The method according to any one of claims 1 to 5, wherein the oxidizing agent is selected from H2O2 and potassium permanganate, or a solution comprising them.

15. The method according to any one of claims 1 to 5, wherein the oxidant is an aqueous solution of hydrogen peroxide having a mass concentration of 10% to 50%.

16. The method according to any one of claims 1 to 5, wherein the oxidant is an aqueous solution of hydrogen peroxide having a mass concentration of 15% to 40%.

17. The method according to any one of claims 1 to 5, wherein the oxidant is an aqueous solution of hydrogen peroxide having a mass concentration of 15% to 35%.

18. The method according to any one of claims 1 to 5, wherein the oxidant is an aqueous solution of hydrogen peroxide having a mass concentration of 20% to 35%.

19. The method according to any one of claims 1 to 5, wherein the oxidant is a 30% by mass concentration hydrogen peroxide aqueous solution.

20. The method according to any one of claims 1 to 5, wherein the oxidant is used in an amount of 5% to 65% by weight of the vegetable oil wax paste to be treated.

21. The method according to any one of claims 1 to 5, wherein the oxidant is used in an amount of 5% to 50% by weight of the vegetable oil wax paste to be treated.

22. The method according to any one of claims 1 to 5, wherein the oxidant is used in an amount of 5% to 45% by weight of the vegetable oil wax paste to be treated.

23. The method according to any one of claims 1 to 5, wherein the oxidant is used in an amount of 10% to 40% by weight of the vegetable oil wax paste to be treated.

24. The method of any one of claims 1 to 5, wherein: The oxidant treatment step further comprises: The mixture obtained after the oxidant treatment is kept warm and allowed to stand for stratification, and the upper wax paste is taken for extraction.

25. The method of claim 24, wherein the upper wax paste is subjected to a dehydration treatment before extraction.

26. The method of claim 25, wherein the dehydration treatment is vacuum drying.

27. The method of claim 26, wherein the vacuum drying is performed at a temperature greater than 100°C.

28. The method of any one of claims 1 to 5, further comprising: The vegetable oil wax paste subjected to the oxidant treatment step is mixed with the solvent for extraction.

29. The method of claim 28, wherein the vegetable oil wax paste subjected to the oxidant treatment step and the solvent have a mixing ratio m:v of 1:1-1:

20.

30. The method of claim 28, wherein the vegetable oil wax paste subjected to the oxidant treatment step and the solvent have a mixing ratio m:v of 1:1-1:

15.

31. The method of claim 28, wherein the vegetable oil wax paste subjected to the oxidant treatment step and the solvent have a mixing ratio m:v of 1:1-1:

10.

32. The method of claim 28, wherein the vegetable oil wax paste subjected to the oxidant treatment step and the solvent have a mixing ratio m:v of 1:1-1:

5.

33. The method of any one of claims 1 to 5, wherein the vegetable oil wax paste is derived from the following oils and fats: rice bran oil, sunflower seed oil, palm oil, palm kernel oil, peanut oil, rapeseed oil, soybean oil, linseed oil, cottonseed oil, safflower seed oil, perilla seed oil, tea seed oil, coconut oil, olive oil, almond oil, apricot kernel oil, corn oil, wheat germ oil, sesame seed oil, evening primrose seed oil, hazelnut oil, pumpkin seed oil, walnut oil, grape seed oil, borage seed oil, sea buckthorn seed oil, tomato seed oil, macadamia nut oil, cocoa butter, algae oil, and combinations thereof.

34. The method of any one of claims 1 to 5, wherein the vegetable oil wax paste is selected from the group consisting of rice bran oil wax paste, sunflower seed oil wax paste, corn oil wax paste, and combinations thereof.

35. The process of any one of claims 1 to 5, wherein the extraction is performed under stirring.

36. The process of any one of claims 1 to 5, wherein the extraction is carried out at a temperature of 20-69°C.

37. The process of any one of claims 1 to 5, wherein the extraction is carried out at a temperature of 30-60°C.

38. The process of any one of claims 1 to 5, wherein the extraction is carried out at a temperature of 40-60°C.

39. The method of any one of claims 1 to 5, wherein the extraction time is 5 min to 180 min.

40. The method of any one of claims 1 to 5, wherein the extraction time is 10 min to 150 min.

41. The method of any one of claims 1 to 5, wherein the extraction time is 20 min to 120 min.

42. The method of any one of claims 1 to 5, wherein the extraction time is 30 min to 90 min.

43. The method according to any one of claims 2, 4 and 5, wherein the mixed liquid obtained after extraction is cooled before the solid-liquid separation step.

44. The method of claim 43, wherein the cooling temperature is -5°C to 30°C.

45. The method of claim 43, wherein the cooling temperature is 0°C-30°C.

46. ​​The method of claim 43, wherein the cooling temperature is 0°C-25°C.

47. The method of claim 43, wherein the cooling temperature is 0°C-20°C.

48. The method of claim 43, wherein the cooling time is not less than 0.5 h.

49. The method of claim 43, wherein the cooling time is not less than 1 hour.

50. The method of claim 43, wherein the cooling time is not less than 1.5 hours.

51. The method of claim 43, wherein the cooling time is not less than 2 hours.

52. The method of claim 3 or 4, wherein the method for removing or recovering the solvent from the liquid phase is rotary evaporation.

53. The method of claim 3 or 5, wherein the method of removing or recovering the solvent from the solid phase places the solid phase in an oven to remove or recover the solvent.

54. The method of claim 53, wherein the oven is an explosion-proof oven.

55. The method of any one of claims 2, 4 and 5, wherein the solid-liquid separation is filtration; wherein the liquid phase is a filtrate and the solid phase is a filter cake.

56. Use of an oxidant in increasing the recovery rate of oil from vegetable oil wax paste or reducing the wax content of oil recovered from vegetable oil wax paste or reducing the oil content of wax recovered from vegetable oil wax paste, The wax paste is treated with an oxidant at a temperature of not less than 60°C and not more than 100°C for 1 h to 5 h; The amount of the oxidant used is 5%-80% of the weight of the wax paste to be treated.

57. The use according to claim 56, wherein the oxidizing agent is selected from H2O2, potassium permanganate, sodium hypochlorite, perchloric acid and combinations thereof, or solutions comprising the same.

58. The use according to claim 57, wherein the solution is an aqueous solution.

59. The use according to claim 56, wherein the oxidizing agent is selected from H2O2 and potassium permanganate, or a solution comprising them.

60. The method of claim 56, wherein the oxidant is an aqueous solution of hydrogen peroxide having a mass concentration of 10% to 50%.

61. The method of claim 56, wherein the oxidant is a hydrogen peroxide aqueous solution having a mass concentration of 15% to 40%.

62. The method of claim 56, wherein the oxidant is a hydrogen peroxide aqueous solution having a mass concentration of 15% to 35%.

63. The method of claim 56, wherein the oxidant is a hydrogen peroxide aqueous solution having a mass concentration of 20% to 35%.

64. The method of claim 56, wherein the oxidant is a 30% mass concentration hydrogen peroxide aqueous solution.

65. The use as described in any one of claims 56-64, wherein the wax paste is a vegetable oil wax paste, wherein the vegetable oil is derived from the following oils and fats: rice bran oil, sunflower seed oil, palm oil, palm kernel oil, peanut oil, rapeseed oil, soybean oil, linseed oil, cottonseed oil, safflower seed oil, perilla seed oil, tea seed oil, coconut oil, olive oil, almond oil, apricot kernel oil, corn oil, wheat germ oil, sesame seed oil, evening primrose seed oil, hazelnut oil, pumpkin seed oil, walnut oil, grape seed oil, borage seed oil, sea buckthorn seed oil, tomato seed oil, macadamia oil, cocoa butter, algae oil and combinations thereof.

66. The use according to any one of claims 56 to 64, wherein the vegetable oil wax paste is selected from the group consisting of rice bran oil wax paste, sunflower seed oil wax paste, corn oil wax paste, and combinations thereof.

67. The use according to any one of claims 56 to 64, wherein the use comprises contacting the wax paste with the oxidant, and extracting the wax paste after contacting with the oxidant with a solvent to obtain the oil or the wax.

68. The use according to claim 67, wherein the solvent is n-hexane.

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