A kind of deacidification adsorbent of grease and preparation method thereof
Technical field
The present invention relates to a kind of deacidification adsorbent of grease and preparation method thereof, be specifically related to a kind of adsorbent that can reduce the vegetable oil acid number and preparation method thereof, belong to grease processing technology field.
Background technology
Usually vegetable crude oil need just can reach edible product oil rank through refining.It is the free fatty of removing in the crude oil that depickling gets main purpose, is an important procedure in the oil refining process, also is the critical process that influences grease refining consumption and product quality.The method of vegetable oil depickling is a lot, mainly contains chemical deacidification, physical deacidification and miscella depickling.Chemical deacidification claims the alkali refining method again, is to add alkali lye that in degummed oil alkali lye and free fatty generation neutralization reaction generate soap stock, centrifugal then removing.Because the soap that generates has stronger adsorption capacity, can bring into soap stock such as the insoluble impurity of a considerable amount of oil such as protein, colloid, trace meter and separated.This method fast, efficiently is applicable to various low acid number greases, and process equipment technology maturation, shortcoming are that the neutral grease loss is bigger, especially are not suitable for the high acid value crude oil.Physical deacidification also claims to distill depickling method and stripping depickling method, and its principle is identical with deodorizing technology, is to feed steam under the condition of heating and high vacuum, and steam is taken free fatty in the oil and low molecular weight volatile thing out of.Compare with the chemical deacidification method, physical deacidification is applicable to high-acid value grease, simple to operate, less energy consumption, the grease loss late can drop to 1.05~1.2%, shortcoming is to crude oil preliminary treatment requirement height and production cost is higher relatively, is not suitable for the high grease of gum level, and high temperature easily produces trans-fatty acid down simultaneously.The miscella depickling be meant grease in solvent (mainly containing n-hexane, isopropyl alcohol, water etc.) with alkali lye mixing depickling, advantage is that the alkaline concentration that uses is low, the centrifugal efficiency height, the neutral grease loss is low, product color is good, and shortcoming is a complex technical process, and solvent consumption and equipment investment are big.Some new lipin deacidifying technology such as biological depickling, chemical resterification depickling, solvent extraction depickling, supercritical extract depickling, membrane separation technique depickling, molecular clock depickling etc. have appearred at present both at home and abroad, but these still are in conceptual phase, not large-scale application.
CN101054245A discloses a kind of metal chelating resin sorbent that utilizes and has separated the method that reclaims aliphatic acid in the water body, it is through after the preliminary treatment with the high salt factory effluent of fatty acid, adjust PH and wastewater temperature, by being filled with the adsorption tower of metal-chelating adsorbent, make fatty acid organic matter selective absorption in the water body with certain flow on adsorbent; Use sodium-chloride water solution as desorbing agent at last,, adsorbed the organic adsorbent desorption and regeneration of the fatty acid in the waste water.This technology is primarily aimed at the fatty acid organic matter in the waste water, and absorbing fats acids organic matter is also recycled, and considers that from function, safety, cost each side this adsorbent is the deacidifying process that can not be used for grease.
CN101264885A discloses a kind of production method of high grade activated carbon from rice husk ash, utilizes rice hull ash to produce alkali lixiviation slag behind the waterglass through washing, and to adopt potassium hydroxide be that activator activates, and makes the gel powder with high adsorptive active carbon through washing, oven dry again.The active carbon of this invention has the good adsorption performance, but is not to be exclusively used in the aliphatic acid that removes in the grease, and it can also adsorb other materials such as neutral grease in a large number except absorbing fats acid.
: JP2004167481 discloses a kind of preparation method of grease sorbing material, and adopting peanut shell, coffee skin of beancurd etc. is raw material, and paraffin is enclosed on the top layer, is mainly used in the grease in the adsorbed oil aqueous mixtures.This grease adsorbent has the good adsorption effect, but it is to adsorb neutral oil and aliphatic acid simultaneously, is not suitable for lipin deacidifying technology.
From the above-mentioned adsorbent that is prepared into by the processing of farm products accessory substance, these adsorbents or exist the neutral oil loss big or exist and be not suitable for lipin deacidifying and handle or have problem such as edible safety are not special-purpose deacidification adsorbent of grease.
On the other hand, China is an agricultural production big country, and agricultural wastes output such as the annual stalk that produces, shell are more than 600,000,000 tons.Along with natural resources shortage day by day, the high-efficiency comprehensive utilization of agricultural wastes more and more comes into one's own, and its recycling has become the important content of Agricultural recycling economy.Oil plant processing byproduct skin (shell) is one of important source of agricultural wastes, the main oil crops annual production of China is about 5,000 ten thousand tons at present, processing byproducts such as the peanut shell that produces, oil tea shell are about more than 3,000,000 tons, but directly abandoned in a large number, cause significant wastage and environmental pollution, therefore make full use of these resources, it is significant to improve oil plant processing enterprise and overall efficiency of agriculture.
Summary of the invention
Technical problem to be solved by this invention is the deficiency that exists at above-mentioned prior art, provides a kind of and can reduce the neutral oil loss, cuts down the consumption of energy, minimizing equipment input, shortens process cycle, is beneficial to comprehensive utilization and is applicable to deacidification adsorbent of grease of suitability for industrialized production and preparation method thereof.
The technical scheme of deacidification adsorbent of grease of the present invention is:
Described deacidification adsorbent is made up of oil crops seed (fruit) shell (skin) that contains alkali compounds, the alkali compounds that described oil crops seed shell contains is 2-35% by weight, and described oil crops seed shell is one or more in oil tea shell, peanut shell, sunflower seed shell, castor-oil plant shell, the walnut shell.
Press such scheme, described alkali compounds is one or more in potassium hydroxide, NaOH, calcium hydroxide, sodium carbonate, the potash.
Press such scheme, described oil crops seed shell is the porosity and looseness shape and through pulverization process, the thickness granularity is 20 orders~100 orders.
Preparation method's technical scheme of deacidification adsorbent of the present invention is:
1) activation---choose oil crops seed (fruit) shell (skin) and clear up, dry under 60~110 ℃ of conditions then, under 150~500 ℃ of conditions, activate again, obtain activator, described oil crops seed shell is one or more in oil tea shell, peanut shell, sunflower seed shell, castor-oil plant shell, the walnut shell;
2) pulverize---activator is crushed to 20 orders~100 orders;
3) absorption---prepare weight concentration and be 5%~45% and contain the aqueous solution of alkali compounds, activator is placed container, add the aqueous solution that contains alkali compounds, the addition that contains the aqueous solution of alkali compounds is 3~15 times of activator volume, stirs 0.5h~5h down at 20~80 ℃;
4) drying---stir back isolated by filtration solids and carry out drying, obtain the deacidification adsorbent of grease product.
Press such scheme, described alkali compounds is one or more in potassium hydroxide, NaOH, calcium hydroxide, sodium carbonate, the potash.
Press such scheme, be 1h~3h the drying time in the described activation processing; Soak time is 1h~7h.
After adsorbent preparation of the present invention was finished, sealed storage was in packaging bag, and this packaging bag can completely cut off outside air, and placed cool place, dry place storage.
The method that deacidification adsorbent of grease of the present invention is used for lipin deacidifying is:
The grease of constant weight is inserted in the special container, add the deacidification adsorbent of grease weight 0.1~6%, fully stir 20min~150min down at 25~110 ℃, speed of agitator is preferably 200~1000 commentaries on classics/min, then centrifugation.Described grease can be rapeseed oil, soybean oil, tea-seed oil, siritch, rice bran oil, sunflower oil, walnut oil, perilla herb oil, sesame oil, cottonseed oil.
The invention has the beneficial effects as follows:
Advantages such as 1) the present invention is a raw material with the shell or the skin of the seed (fruit) of oil crops, and the preparation deacidification adsorbent of grease can be realized the high-efficiency comprehensive utilization of discarded object, and it is better to have environmental-protecting performance simultaneously, and cost is lower.
2) to have preparation technology simple for deacidification adsorbent of grease of the present invention, and characteristics such as advantages of good adsorption effect can guarantee adsorbent good adsorption ability and deacidification effect by conditions such as control activation temperature, solution concentrations.
3) applicability of the present invention is strong, can be widely used in different types of vegetable oil, and is suitable for the plant oil product of low acid number and high acid value simultaneously.
4) to be used for the technological operation and the equipment of lipin deacidifying simple in the present invention, and the cycle is short, solvent-free loss, and energy consumption and production cost are low, replace existing traditional alkali refining method to use without any need for the equipment input.
Specific embodiments
Embodiment 1:
Take by weighing the 2000g peanut shell, after the cleaning removal of impurities,, under 300 ℃ of conditions, activate 5h then, be crushed to 30 orders after the cooling at 80 ℃ of following dry 3h.Take by weighing the 100g activator in special container, the adding weight concentration is 15% potassium hydroxide solution, and addition is 12 times of activator volume, be heated to 50 ℃, fully stir 5h, then isolated by filtration, 105 ℃ of following drying solid thing 1h obtain the deacidification adsorbent of grease product I.What take by weighing the 500g acid number and be 1.95mgKOH/g comes unstuck rapeseed oil in special container, the deacidification adsorbent I that adds grease weight 2%, be warming up to 60 ℃, under 500 commentaries on classics/min, stir 50min, obtain the depickling rapeseed oil after the centrifugation, measuring its acid number is 0.20mgKOH/g, neutral oil yield 97.7%.
Embodiment 2:
Take by weighing 1000g oil tea shell, at 95 ℃ of following dry 2h, under 400 ℃ of conditions, activate 4h then after the cleaning removal of impurities, cool off and be crushed to 40 orders.Take by weighing the 100g activator in special container, the adding weight concentration is 20% sodium hydroxide solution, and addition is 8 times of activator volume, be heated to 40 ℃, fully stir 4h, isolated by filtration, 105 ℃ of following drying solid thing 1h obtain deacidification adsorbent of grease product I I.What take by weighing the 500g acid number and be 2.33mgKOH/g comes unstuck tea-seed oil in special container, adds the deacidification adsorbent II of grease weight 2.0%, is warming up to 50 ℃, under 500 commentaries on classics/min, stir 60min, the centrifugation tea-seed oil, the acid number of measuring tea-seed oil is 0.18mgKOH/g, neutral oil yield 97.3%.
Embodiment 3:
Take by weighing the 2000g sunflower seed shell, at 105 ℃ of following dry 1h, under 350 ℃ of conditions, activate 6h then after the cleaning removal of impurities, be crushed to 60 orders after the cooling, obtain activator.Take by weighing the 100g activator in special container, add weight concentration and be 25% solution of potassium carbonate, addition is 15 times of activator volume, fully stirs 5h under the room temperature, isolated by filtration then, and 105 ℃ of following drying solid thing 1h obtain deacidification adsorbent of grease product I II.The degummed flax seeds oil that takes by weighing the 500g acid number and be 2.86mgKOH/g is in special container, the deacidification adsorbent III that adds grease weight 1%, be warming up to 70 ℃, under 500 commentaries on classics/min, stir 30min, the centrifugation linseed oil, the acid number of measuring linseed oil is 0.29mgKOH/g, neutral oil yield 96.3%.
Embodiment 4:
Take by weighing the 300kg peanut shell, after the cleaning removal of impurities,, under 300 ℃ of conditions, activate 5h then, be crushed to 30 orders after the cooling at 105 ℃ of following dry 1h.Take by weighing the 135kg activator in special container, the adding weight concentration is 15% sodium hydroxide solution, and addition is 12 times of activator volume, be heated to 50 ℃, fully stir 5h, then isolated by filtration, 105 ℃ of following drying solid thing 1.5h obtain deacidification adsorbent of grease product I V.What take by weighing the 5000kg acid number and be 1.91mgKOH/g comes unstuck rapeseed oil in special container, the deacidification adsorbent IV that adds grease weight 1.5%, be warming up to 40 ℃, under 500rpm/min, stir 40min, obtain rapeseed oil after the depickling after the centrifugation, measuring its acid number is 0.19mgKOH/g, neutral oil yield 97.5%.