CN103224236B - Peanut shell activated carbon for removing toxins in peanut oil and preparation method thereof - Google Patents
Peanut shell activated carbon for removing toxins in peanut oil and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of activated carbon, and particularly relates to a peanut shell activated carbon for removing toxins in peanut oil and a preparation method thereof. The peanut shell activated carbon is prepared by carrying out pretreatment, extrusion molding, carbonization and activation on peanut shells. The preparation method comprises the following steps: pretreatment: carrying out hydrothermal treatment on the peanut shells, and pulverizing; extrusion molding: carrying out pressure molding with a granulator to obtain cylindrical granules of which the diameters are 4-8 mm and the lengths are 10-20 mm; heating, cooling in the absence of oxygen, crushing and screening to control the granule diameters at 1-3 mm; and introducing isothermal superheated vapor, storing in a sealed environment, and cooling to obtain the finished product. The activated carbon is prepared from the peanut shells which are accessible raw materials, thereby implementing utilization of waste peanut shells; and the obtained peanut shell activated carbon has the advantages of large specific area and small pore size, can simultaneously adsorb benzopyrene, aflatoxin and other harmful substances, and can prevent the peanut oil from oxidative rancidity.
Description
Technical field
The invention belongs to technical field of active carbon, be specifically related to a kind ofly remove Activated Carbon Made from Peanut Shells of toxin in peanut oil and preparation method thereof.
Background technology
Peanut oil is that China's ordinary people eats the edible oil maximum with consumption, but the security of edible oil based on peanut oil allows of no optimist.Peanut oil raw material is subject to flavus etc. and infects in transporting procedures, after processing without in the peanut oil of detoxification process often containing the aflatoxin exceeded standard (mainly AFB
1), in the course of processing, high temperature easily produces benzopyrene, because Vegetable oil lipoprotein contains multiple unsaturated double-bond, in the storage course of processing, easily oxidative rancidity occurs.Aflatoxin and benzopyrene exceed standard the most common and extensive in peanut oil pollutes, and aflatoxin is the compound that one group of chemical structure is similar, and the basic structure of aflatoxin is two furan nucleuss and tonka bean camphor, and B1 is the derivative of dihydrofuran coumarin.Namely containing a bifuran and a coumarin (tonka bean camphor).Benzopyrene is the organic compound that a class has obvious carcinogenesis.It is the polycyclic arene compound be combined into by a phenyl ring and a pyrene molecule.And the oxidative rancidity of grease is because unsaturated composition is wherein by the effect generation autoxidation of oxygen in air, moisture or mould, generates superoxide and then be degraded to the complex mixture of volatile aldehyde, ketone, carboxylic acid, and produce niff.
At present, in peanut oil, the minimizing technology of benzopyrene, aflatoxin mainly comprises heavy dose of uviolizing, alkali cleaning removing toxic substances and biological enzyme, but complex process, cost and energy consumption high, removal effect is unstable, and it is rotten easily to cause Oxidation of Fat and Oils, affects local flavor etc.Can adopt physisorphtion in addition, take gac as sorbent material, toxic substance in grease comprised pigment and gets rid of.But gac at present on the market, aperture is large, specific surface area is relatively little, adsorptive is single, and on average every 1 kilogram of gac can adsorb the peanut oil of 1.5 kilograms, adds production cost to a certain extent, affects yield.
At present in the selection of activated carbon raw material, great many of experiments finds, with the hard coal in the coconut husk in plant raw material and mineral substance raw material and the made charcoal-stripped the best of refinery coke.This project Pericarppium arachidis hypogaeae prepares gac, and raw material is easy to get, and operating procedure is easy.Peanut is the main oil crops of China, and its ultimate production and export volume all occupy first place in the world.China's peanut gross annual output amount reaches about 1,500 ten thousand tons, account for 42% of Peanut ultimate production, about can produce 5,000,000 tons of Pericarppium arachidis hypogaeaes every year. and these Pericarppium arachidis hypogaeaes do not have or be seldom used effectively, and cause the significant wastage of resource, therefore study Pericarppium arachidis hypogaeae preparing active carbon significant.
Research both at home and abroad about method for preparation of active carbon has relevant report, and people's grand celebration refinery cokes such as Wu Ming platinum are raw material is that activator obtains high performance active carbon with NaOH.The people such as Song Yan utilize Panjin refinery coke to take KOH as activator, and preparation specific surface area is 3730m
2the active carbon with high specific surface area of/g.But this type of Activated Carbon Production cost intensive, is only limitted to the fields such as medicine, electronics, gas adsorption storage.The people such as Zhao Naiqin prepare in the process of activated carbon process in research and utilization dedusting ash, find that powdered carbon is first through normal temperature ammonia salt pretreatment, can reduce the ash content of gac, improve the specific surface area of gac.The people such as Marsh and Rand use carbon dioxide activation mix Fe or Ni particulate in poly-furfuralcohol after, make the activated carbon fiber of mesopore prosperity.Resol and polybutene fourth fat mix with 1:1 ratio by Ozaki etc. in methyl alcohol, obtained mesopore activated carbon.Gac is one of focus of environmental-protection adsorption investigation of materials.Along with the development to gac investigation and application, sight is turned to the new resources finding gac by people.
Pericarppium arachidis hypogaeae is a kind of excellent gac resource, China's Pericarppium arachidis hypogaeae resource is very abundant, but Pericarppium arachidis hypogaeae is mostly as fuel at present, limited comprehensive development and utilization is mainly produces medicine, processing feed, culturing edible fungus, manufacture composite sheet etc., but added value is low, even new environmental pollution can be caused.
Summary of the invention
For the deficiencies in the prior art, the object of this invention is to provide a kind of Activated Carbon Made from Peanut Shells removing toxin in peanut oil, the gac specific surface area of gained is large, aperture is little, the objectionable impurities such as benzopyrene, aflatoxin can be adsorbed simultaneously, prevent peanut oil oxidative rancidity, and provide its preparation method, operating procedure is easy.
The Activated Carbon Made from Peanut Shells of toxin in removal peanut oil of the present invention, Activated Carbon Made from Peanut Shells is made up through pre-treatment, extrusion molding, carbonization and activation of Pericarppium arachidis hypogaeae.
The aperture of Activated Carbon Made from Peanut Shells is 0.2-10nm; Specific surface area is 1000-2000m
2/ g, the preferred 1500-1700m of specific surface area
2/ g.The Activated Carbon Made from Peanut Shells aperture that the present invention obtains is less than normal activated carbon, and specific surface area is greater than normal activated carbon, to the adsorptive power of toxic substance also beyond normal activated carbon.If aperture is too large, the grease molecules easily in absorption peanut oil, affects the output of peanut oil.
The preparation method of the Activated Carbon Made from Peanut Shells of toxin in described removal peanut oil, comprises the following steps:
(1) pre-treatment: carry out hydrothermal treatment consists to Pericarppium arachidis hypogaeae, pulverizes;
(2) extrusion molding: then obtaining diameter with nodulizer compression moulding is 4-8mm, and length is the cylindrical pellet of 10-20mm;
(3) carbonization: heated by the cylindrical pellet of step (2) gained, then starvation cooling down, fragmentation is sieved, and particle diameter controls at 1-3mm;
(4) activate: the heating particles obtained after step (3) being processed, passes into isothermal superheated vapour, and sealing is preserved, and then cools, obtains finished product.
In step (1), hydrothermal treatment consists is specially: carry out 175-185 DEG C of saturated steam thermal treatment 2-3h to Pericarppium arachidis hypogaeae, preferred 2.5h.Because Pericarppium arachidis hypogaeae organic content is enriched, need special activation treatment, to reduce organic content, hydrothermal treatment consists can remove the organic matter in Pericarppium arachidis hypogaeae, adopt hydrothermal treatment consists simultaneously, change the relative content of xylogen, Mierocrystalline cellulose and hemicellulose in Pericarppium arachidis hypogaeae, improve the structure of Pericarppium arachidis hypogaeae, increase the output of gac.
Cross the sieve of aperture 2mm after pulverizing in step (1), then add moisture mixing, make its moisture content control at 4-12%, preferred 6-10%, more preferably 8%, be then placed in encloses container and place 72-84h.Control the moisture content of Pericarppium arachidis hypogaeae after hydrothermal treatment consists, keep 72-84 hour at a certain temperature, stabilize Pericarppium arachidis hypogaeae internal structure, make the arrangement of carbon atom in Pericarppium arachidis hypogaeae more neat, the activated carbon pore size obtained is little and close.Different moisture contents affects yield and the character of gac, when moisture content is 8%, the yield of gac is maximum, reach maximum when hardness is between 6-10%, and affect little on volume density and apparent density, therefore preferably moisture content is that 6-10% prepares gac.When moisture content is 8%, productive rate reaches maximum and energy consumption is minimum.For reducing production cost, increase Activated Carbon Production amount, moisture content preferably 8% in hydrothermal treatment consists.
Obtaining diameter with nodulizer compression moulding in step (2) is 4-8mm, and length is the cylindrical pellet of 10-20mm, ensures to remove organic matter to greatest extent when next step carbonizes.Nodulizer temperature controls at 95-105 DEG C.
In step (3), heating is specially: with the heating rate of per minute 2 DEG C to 450-650 DEG C, preferably 600 DEG C.From the view point of porosity, pore volume total when carbonization temperature is 600 DEG C is lower.
Step is heated to be in (4): with the heating rate of per minute 19-21 DEG C to 840-860 DEG C.
In step (4), the mass ratio of the particle that isothermal superheated vapour and step (3) obtain after processing is 2.5-3.5:1.Isothermal superheated vapour is as oxygenant.
The time that in step (4), sealing is preserved is 80-100 minute.The Activated Carbon Made from Peanut Shells that the present invention prepares can remove the toxin in peanut oil, especially can the toxic compounds such as adsorption of aflatoxin, benzopyrene, and reduces superoxide in grease.During use, the gac prepared is joined in the peanut oil work in-process after dewaxing, low frequency ultrasound can be utilized to vibrate and stir, gac fully be mixed with grease, removes gac after for some time and obtain processed oil.
In sum, the present invention has the following advantages:
(1) the Activated Carbon Made from Peanut Shells aperture that obtains of the present invention is little, specific surface area large, has good adsorption effect and oil consumption is low to objectionable impurities in peanut oil.
(2) the present invention utilize discarded Pericarppium arachidis hypogaeae take the lead in exploitation be applicable to absorption peanut grease in toxic substance, reduce peroxide level, prevent oxidative rancidity.
(3) from Pericarppium arachidis hypogaeae, prepare activated carbon raw material to be easy to get, achieve the utilization of waste material to planting base Pericarppium arachidis hypogaeae, meet the demand for development of low-carbon (LC), recycling economy.Operating procedure is easy, and therefore the gac of preparation has wide development & application prospect.
(4) aflatoxin and benzopyrene annoying peanut oil industry as two large carcinogenic substances always, present invention efficiently solves this problem, improve product safety quality.
Embodiment
Below in conjunction with embodiment, the present invention will be further described.
Embodiment 1
(1) pre-treatment: the Pericarppium arachidis hypogaeae cleaned up is placed in 180 DEG C of flowing steam environment and processes 2h, pulverized 2mm aperture sieve, then add moisture mixing, regulate moisture content to 4%, room temperature preservation 72h in encloses container.
(2) extrusion molding: with nodulizer, peanut shell granular being pressed into diameter on the flat board of 100 DEG C is 6mm, and length is the cylindrical pellet of 12mm.
(3) carbonization: carbonization is carried out in retort bottle, be energized Pericarppium arachidis hypogaeae cylinder with the heating rate to 450 DEG C of 2 DEG C/min respectively, then under sealing condition, be cooled to room temperature, pulverize and sieve, particle diameter controls at 1mm.
(4) activate: the particle after carbonization is placed in retort bottle, add that process furnace put into by steam superheating coil, with the heating rate to 840 DEG C of per minute 20 DEG C, sealing is preserved, continue to pass into isothermal superheated vapour and sealing preservation 90min, and guarantee that the mass ratio of the particle obtained after isothermal superheated vapour and step (3) process is at 3:1, be then cooled to the temperature taking-up identical with surrounding environment and obtain finished product.
Embodiment 2
(1) raw materials pretreatment: the Pericarppium arachidis hypogaeae cleaned up is placed in 178 DEG C of flowing steam environment and processes 2.2h, pulverized 2mm aperture sieve, then add moisture mixing, regulate moisture content to 6%, room temperature preservation 78h in encloses container.
(2) extrusion molding: with nodulizer, peanut shell granular being pressed into diameter on the flat board of 100 DEG C is 6mm, and length is the cylindrical pellet of 18mm.
(3) carbonization: carbonization is carried out in retort bottle, be energized Pericarppium arachidis hypogaeae cylinder with the heating rate to 500 DEG C of 2 DEG C/min respectively, then under sealing condition, be cooled to room temperature, pulverize and sieve, particle diameter controls at 3mm.
(4) activate: the particle after carbonization is placed in retort bottle, add that process furnace put into by steam superheating coil, with the heating rate to 850 DEG C of per minute 20 DEG C, continue to pass into isothermal superheated vapour and sealing preservation 100min, and guarantee that the mass ratio of the particle obtained after isothermal superheated vapour and step (3) process is at 3.5:1, be then cooled to the temperature taking-up identical with surrounding environment and obtain finished product.
Embodiment 3
(1) raw materials pretreatment: the Pericarppium arachidis hypogaeae cleaned up is placed in 175 DEG C of flowing steam environment and processes 2.5h, pulverized 2mm aperture sieve, then add moisture mixing, regulate moisture content to 8%, room temperature preservation 80h in encloses container.
(2) extrusion molding: with nodulizer, peanut shell granular being pressed into diameter on the flat board of 95 DEG C is 6mm, and length is the cylindrical pellet of 20mm.
(3) carbonization: carbonization is carried out in retort bottle, be energized Pericarppium arachidis hypogaeae cylinder with the heating rate to 600 DEG C of 2 DEG C/min respectively, then under sealing condition, be cooled to room temperature, pulverize and sieve, particle diameter controls at 2.5mm.
(4) activate: the particle after carbonization is placed in retort bottle, add that process furnace put into by steam superheating coil, with the heating rate to 860 DEG C of per minute 21 DEG C, continue to pass into isothermal superheated vapour and sealing preservation 80min, and guarantee that the mass ratio of the particle obtained after isothermal superheated vapour and step (3) process is at 2.5:1, be then cooled to the temperature taking-up identical with surrounding environment and obtain finished product.
Embodiment 4
(1) raw materials pretreatment: the Pericarppium arachidis hypogaeae cleaned up is placed in 185 DEG C of flowing steam environment and processes 3h, pulverized 2mm aperture sieve, then add moisture mixing, regulate moisture content to 5%, room temperature preservation 84h in encloses container.
(2) extrusion molding: with nodulizer, peanut shell granular being pressed into diameter on the flat board of 105 DEG C is 4mm, and length is the cylindrical pellet of 10mm.
(3) carbonization: carbonization is carried out in retort bottle, be energized Pericarppium arachidis hypogaeae cylinder with the heating rate to 600 DEG C of 2 DEG C/min respectively, then under sealing condition, be cooled to room temperature, pulverize and sieve, particle diameter controls at 2mm.
(4) activate: the particle after carbonization is placed in retort bottle, add that process furnace put into by steam superheating coil, with the heating rate to 850 DEG C of per minute 19 DEG C, continue to pass into isothermal superheated vapour and sealing preservation 90min, and guarantee that the mass ratio of the particle obtained after isothermal superheated vapour and step (3) process is at 3:1, be then cooled to the temperature taking-up identical with surrounding environment and obtain finished product.
Embodiment 5
(1) raw materials pretreatment: the Pericarppium arachidis hypogaeae cleaned up is placed in 182 DEG C of flowing steam environment and processes 2.4h, pulverized 2mm aperture sieve, then add moisture mixing, regulate moisture content to 12%, room temperature preservation 76h in encloses container.
(2) extrusion molding: with nodulizer, peanut shell granular being pressed into diameter on the flat board of 100 DEG C is 8mm, and length is the cylinder of 14mm.
(3) carbonization: carbonization is carried out in retort bottle, be energized Pericarppium arachidis hypogaeae cylinder with the heating rate to 550 DEG C of 2 DEG C/min respectively, then under sealing condition, be cooled to room temperature, pulverize and sieve, particle diameter controls at 2.2mm.
(4) activate: the particle after carbonization is placed in retort bottle, add that process furnace put into by steam superheating coil, with the heating rate to 845 DEG C of per minute 20 DEG C, continue to pass into isothermal superheated vapour and sealing preservation 90min, and guarantee that the mass ratio of the particle obtained after isothermal superheated vapour and step (3) process is at 3:1, be then cooled to the temperature taking-up identical with surrounding environment and obtain finished product.
Comparative example
Activated Carbon Made from Peanut Shells Pericarppium arachidis hypogaeae, normal activated carbon and embodiment 1-5 prepared joins in the peanut oil work in-process after dewaxing respectively, utilize low frequency ultrasound to vibrate to stir, gac is fully mixed with grease, then removes gac and obtain processed oil.Have studied the physical property of different sorbent material and the adsorptive power to aflatoxin and benzopyrene, result is as shown in table 1.
The physical properties of the different sorbent material of table 1 and the adsorption effect to aflatoxin and benzopyrene
As can be seen from Table 1, the Activated Carbon Made from Peanut Shells aperture that the present invention obtains is less than normal activated carbon and specific surface area is far longer than normal activated carbon, to the adsorptive power of toxic substance also beyond normal activated carbon.
Claims (6)
1. remove a preparation method for the Activated Carbon Made from Peanut Shells of toxin in peanut oil, it is characterized in that: Activated Carbon Made from Peanut Shells is made up through pre-treatment, extrusion molding, carbonization and activation of Pericarppium arachidis hypogaeae; The aperture of Activated Carbon Made from Peanut Shells is 0.2-10nm, and specific surface area is 1000-2000m
2/ g;
The preparation method of the Activated Carbon Made from Peanut Shells of toxin in described removal peanut oil, comprises the following steps:
(1) pre-treatment: carry out hydrothermal treatment consists to Pericarppium arachidis hypogaeae, pulverizes;
(2) extrusion molding: then obtaining diameter with nodulizer compression moulding is 4-8mm, and length is the cylindrical pellet of 10-20mm;
(3) carbonization: heated by the cylindrical pellet of step (2) gained, then starvation cooling down, fragmentation is sieved, and particle diameter controls at 1-3mm;
(4) activate: the heating particles obtained after step (3) being processed, passes into isothermal superheated vapour, and sealing is preserved, and then cools, obtains finished product;
Wherein:
In step (1), hydrothermal treatment consists is specially: carry out 175-185 DEG C of saturated steam thermal treatment 2-3h to Pericarppium arachidis hypogaeae;
Cross the sieve of aperture 2mm after pulverizing in step (1), then add moisture mixing, make its moisture content control at 4-12%, be then placed in encloses container and place 72-84h.
2. the preparation method of the Activated Carbon Made from Peanut Shells of toxin in removal peanut oil according to claim 1, is characterized in that: in step (2), nodulizer temperature controls at 95-105 DEG C.
3. the preparation method of the Activated Carbon Made from Peanut Shells of toxin in removal peanut oil according to claim 1, is characterized in that: in step (3), heating is specially: with the heating rate of per minute 2 DEG C to 450-650 DEG C.
4. the preparation method of the Activated Carbon Made from Peanut Shells of toxin in removal peanut oil according to claim 1, is characterized in that: step is heated to be in (4): with the heating rate of per minute 19-21 DEG C to 840-860 DEG C.
5. the preparation method of the Activated Carbon Made from Peanut Shells of toxin in removal peanut oil according to claim 1, is characterized in that: in step (4), the mass ratio of the particle that isothermal superheated vapour and step (3) obtain after processing is 2.5-3.5:1.
6. the preparation method of the Activated Carbon Made from Peanut Shells of toxin in removal peanut oil according to claim 1, is characterized in that: the time that in step (4), sealing is preserved is 80-100 minute.
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Families Citing this family (11)
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| CN105776211A (en) * | 2014-12-24 | 2016-07-20 | 桂林电子科技大学 | Peanut shell active carbon and preparation process thereof |
| CN104998620B (en) * | 2015-06-30 | 2017-06-06 | 南京工业大学 | A kind of modified peanut charcoal/aluminium polychloride sludge composite adsorbing material |
| CN105623849A (en) * | 2016-03-28 | 2016-06-01 | 广西壮族自治区林业科学研究院 | Method for removing aflatoxin in peanut oil |
| CN106701312A (en) * | 2017-01-08 | 2017-05-24 | 山东乐悠悠花生油科技有限公司 | Aqueous enzymatic method extraction process of high-quality peanut oil |
| CN108128773B (en) * | 2017-12-29 | 2020-06-23 | 中南民族大学 | Method for preparing electrode carbon material for electrochemical capacitor by using peanut shells |
| CN108160035A (en) * | 2018-01-16 | 2018-06-15 | 于铭谦 | Air purifying preparation and preparation method thereof |
| CN109331788B (en) * | 2018-10-29 | 2021-09-28 | 山东省农业科学院农业质量标准与检测技术研究所 | Adsorbent for removing aflatoxin in peanut oil and preparation method thereof |
| CN111330539B (en) * | 2018-12-19 | 2022-08-26 | 丰益(上海)生物技术研发中心有限公司 | Composite solid adsorbent and method for purifying grease |
| CN110951540A (en) * | 2019-11-19 | 2020-04-03 | 山东华胜检验检测技术有限公司 | Method for removing aflatoxin by physical adsorption |
| CN114381331A (en) * | 2022-01-22 | 2022-04-22 | 青岛天祥食品集团有限公司 | Five-fresh peanut oil and preparation process thereof |
| CN114768758A (en) * | 2022-03-30 | 2022-07-22 | 山东省花生研究所 | Peanut shell-based biochar material for adsorbing aflatoxin, and preparation method and application thereof |
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