CN111330539A - Composite solid adsorbent and method for purifying grease - Google Patents
Composite solid adsorbent and method for purifying grease Download PDFInfo
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- CN111330539A CN111330539A CN201811558067.1A CN201811558067A CN111330539A CN 111330539 A CN111330539 A CN 111330539A CN 201811558067 A CN201811558067 A CN 201811558067A CN 111330539 A CN111330539 A CN 111330539A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
- B01J20/205—Carbon nanostructures, e.g. nanotubes, nanohorns, nanocones, nanoballs
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/10—Refining fats or fatty oils by adsorption
Abstract
The invention relates to a composite solid adsorbent, which comprises: activated carbon and nanomaterials; the activated carbon has a pH of 9 to 14. The invention also relates to a method for purifying the grease by using the adsorbent.
Description
Technical Field
The invention relates to the field of oil preparation, in particular to an adsorbent for adsorbing and purifying impurities in oil and a method for purifying oil by using the adsorbent.
Background
3-chloro-1, 2-propanediol (3-MCPD) esters are esters of 3-chloro-1, 2-propanediol in which a single hydroxyl group or two hydroxyl groups are simultaneously linked to a long-chain fatty acid. In recent years, researchers have found 3-chloropropanediol esters in many foods, non-limiting examples of which include bread, coffee, refined vegetable oils, baby milk, crackers, malt products, french fries, donuts, pickled olives, herrings, and the like. Wherein the diester content is high and accounts for 85% of the total amount, and the monoester accounts for 15% at most. In 2008, 3-chloropropanediol ester was also detected in breast milk at a content of < 300-.
Glycidyl Ester (GE) is an esterification product of fatty acid and glycidol, and is usually formed along with 3-chloropropanediol ester in the oil refining process, and if the content of the 3-chloropropanediol ester in the oil is higher, the content of the glycidyl ester is also higher. Glycidyl ester is a genotoxic carcinogen, IARC identifies it as a human grade 2A carcinogen, and German DGF identifies it as a class 2 carcinogen when studying the health hazards of MAK chemicals. In 2006 to 2008, the german scholars Weisshaar et al (Food addit. continuous., 2006,23, 1290-. In 2008, a diacylglycerol-rich fat product (ECONA) of KAO was exposed to very high levels of glycidyl esters and forced off-shelf. Considering the potential safety risks caused by both, the german food safety evaluation organization BfR postulates: during digestion in humans, 3-chloropropanol esters and glycidyl esters will hydrolyze to 100% to 3-chloropropanol and glycidol. This would be far in excess of safety standards, such as infant milk powder 12.5-20 times TDI (maximum daily intake), and adult vegetable fat 5-10 times TDI.
In order to meet the strict requirements of the food industry on the content of glycidyl ester and 3-chloropropanediol ester, different technologies have been tried to purify oil products.
The prior art includes the technology of reducing MCPD in grease by treating grease with an adsorbent and/or alkali, wherein the alkali used is hydroxide, carbonate, bicarbonate of alkali metal or alkaline earth metal, and the adsorbent is commonly used in the food field, such as clay, silicate, etc. There has been reported a technology for purifying oil and fat by mixing adsorbents which are conventional in the field of food to prepare a chromatography column, but there is no description of a combination of modified activated carbon having a pH of 9 to 14 and a nanomaterial, which is specifically defined in the present invention.
There are also reports that the grease may be further treated with silica gel or activated carbon, organic acid solution, polar solvent, etc. after being subjected to decoloring and deodorizing treatment to reduce the content of 3-MCPD ester.
Other research has been directed to other purification mechanisms that do not employ adsorbents. For example, WO2014/012759a1 provides a method for reducing the 2-/3-MCPD and glycidyl ester content of refined triglyceride oils without using an adsorbent, by heating the fats under reduced steam pressure after mixing the fats with the alkali using only the alkali. The steam stripping technology is used for realizing the remarkable reduction of the contents of 2-/3-MCPD and glycidyl ester in the grease, and ensuring that the esterification degree in the product is lower than 60 percent.
However, the above methods have some limitations, such as limited purification capability for 3-MCPD and GE, which cannot easily achieve impurity levels in the oils and fats that meet the relevant requirements, and some purification operations may cause side reactions such as saponification of the oils and fats, further introducing new impurities. Accordingly, there is a need for improvements in the prior art that overcome the deficiencies of the prior art.
The nanometer particle is superfine particle with the particle size of nanometer level (1-100nm), the size of the nanometer particle is larger than an atomic cluster and smaller than that of a common block material, the nanometer particle is in the middle field between a microscopic system and a macroscopic system, and the nanometer particle belongs to the mesoscopic category. At present, no report is available about the combination of nanoscale materials and specific pH value modified activated carbon to realize the effective removal of 3-MCPD and GE in grease.
According to the scheme of the invention, a novel compound adsorbent is obtained by combining a nano-grade material and modified activated carbon with a specific pH value, the adsorbent can effectively remove 3-MCPD and GE in grease, and simultaneously the problem of saponification of the grease in the purification process is avoided.
Disclosure of Invention
According to a first aspect of the present invention, there is provided a composite solid adsorbent comprising:
(i) activated carbon; and
(ii) a nanomaterial;
the activated carbon has a pH of 9 to 14, preferably 9.1 to 13.
According to a preferred embodiment of the present invention, the weight ratio of the activated carbon to the nanomaterial is 1:1 to 1000:1, preferably 1:1 to 100:1, and more preferably 2:1 to 100: 1.
According to another preferred embodiment of the present invention, the activated carbon is an activated carbon modified by the steps of: an unmodified raw activated carbon is provided, which is treated with an alkaline agent to obtain a modified activated carbon having a pH of 9 to 14, preferably 9.1 to 13, more preferably 9.5 to 13.
According to another preferred embodiment of the present invention, the operation of treating the raw activated carbon with the alkaline agent comprises the steps of:
a. treating the raw material active carbon by using an alkaline reagent;
b. separating the alkaline reagent from the treated raw material active carbon;
c. washing the treated raw activated carbon to obtain activated carbon with a pH value of 9-14, preferably 9.1-13, more preferably 9.5-13, preferably drying the treated raw activated carbon, further preferably crushing the treated dried raw activated carbon, further preferably sieving the treated dried crushed raw activated carbon, wherein the sieving is preferably performed by using a sieve with 50-800 meshes, preferably using a sieve with 150-400 meshes, and further preferably using a sieve with 200-250 meshes;
the alkaline agent is selected from aqueous solutions or suspensions in water of the following compounds: CaO, Ca (OH)2、NaOH、KOH、Al2O3Aluminum hydroxide, MgO, magnesium hydroxide, ammonia, lithium hydroxide, copper hydroxide, iron hydroxide, ferrous hydroxide, copper hydroxide, carbonates, bicarbonates, and combinations of two or more thereof;
step c uses water for washing.
According to another preferred embodiment of the present invention, the nanomaterial is selected from a nanocarbon material, a nanometal material, or a mixture thereof.
According to another preferred embodiment of the present invention, the shape of the nanocarbon material is spherical, irregular granular, tubular or sheet, and the kind thereof is selected from one or more of the following: fullerene, nano-diamond, carbon nano-tube, graphene and graphene oxide, reduced graphene oxide, graphene quantum dot and carbon dot which are derivatives of graphene; single-walled, double-walled or multi-walled carbon nanotubes having a diameter of 60nm or less are preferable, and graphene and derivatives thereof having a thickness of 10nm or less are preferable.
According to another preferred embodiment of the present invention, the shape of the nano-metallic material is nano-metallic particles or nano-metallic clusters, and the kind thereof is selected from the group consisting of: silver, gold, copper, ruthenium, rhodium, palladium, osmium, iridium, platinum, alloys of the above elements, and alloys of two or more of the above elements with each other; preferably selected from copper, silver alloys, gold and gold alloys.
In a second aspect of the present invention, there is provided a method for purifying fats and oils, comprising:
mixing the composite solid adsorbent of the invention with oil and fat containing impurities, so that the adsorbent adsorbs at least part of the impurities;
separating the adsorbent having adsorbed at least a portion of the impurities from the fat.
According to an embodiment of the second aspect of the invention, the impurities comprise one or both of chloropropanol esters and glycidyl esters. According to one embodiment of the present invention, the method of the present invention can achieve substantially complete removal of chloropropanol esters and glycidyl esters from fats and oils, by "substantially complete removal" is meant removal of 50 wt% or more, preferably 55 wt% or more, preferably 60 wt% or more, even more preferably 65 wt% or more, even 70 wt% or more, 75 wt% or more, or 80 wt% or more of either or both of chloropropanol esters and glycidyl esters.
According to a preferred embodiment of the invention, the method of the invention comprises at least one of the following features 1) to 5):
1) the amount of the adsorbent is 0.1 to 20% by weight, preferably 0.1 to 10% by weight, more preferably 0.1 to 5% by weight, and still more preferably 0.1 to 3.5% by weight, based on the total weight of the oil or fat;
2) the adsorbent is mixed with the grease containing impurities at the temperature of 150 ℃ to 250 ℃, preferably 160 ℃ to 230 ℃;
3) mixing the adsorbent with the oil containing impurities for at least 30 minutes, preferably 60-180 minutes;
4) mixing the adsorbent with oil containing impurities, and adjusting the temperature to be below 80 ℃; and
5) separating the adsorbent having adsorbed at least a portion of the impurities from the oil or fat by filtration or centrifugation.
According to another preferred embodiment of the present invention, in the process of the present invention, the impurities comprise one or both of chloropropanol ester and glycidyl ester, preferably the grease does not undergo significant saponification throughout the process to yield soap species of no more than 100 ppm; preferably, no saponification reaction occurs and no soap is formed.
In a third aspect of the present invention, there is provided a grease prepared after purification by the method of the present invention, preferably, the sum of the contents of chloropropanol ester and glycidyl ester in the grease is less than 5ppm, preferably less than 3ppm, and more preferably less than 1 ppm.
Detailed Description
The "ranges" disclosed herein are in the form of lower and upper limits. There may be one or more lower limits, and one or more upper limits, respectively. The given range is defined by the selection of a lower limit and an upper limit. The selected lower and upper limits define the boundaries of the particular range. All ranges that can be defined in this manner are inclusive and combinable, i.e., any lower limit can be combined with any upper limit to form a range. For example, ranges of 60-120 and 80-110 are listed for particular parameters, with the understanding that ranges of 60-110 and 80-120 are also contemplated. Furthermore, if the minimum range values 1 and 2 are listed, and if the maximum range values 3, 4, and 5 are listed, the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5.
In the present invention, unless otherwise stated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, a numerical range of "0 to 5" indicates that all real numbers between "0 to 5" have been listed herein, and "0 to 5" is only a shorthand representation of the combination of these numbers.
The term "two" as used herein means "at least two" if not otherwise specified.
In the present invention, all embodiments and preferred embodiments mentioned herein may be combined with each other to form a new technical solution, if not specifically stated.
In the present invention, all the technical features mentioned herein and preferred features may be combined with each other to form a new technical solution, if not specifically stated.
In the present invention, all the steps mentioned herein may be performed sequentially or randomly, if not specifically stated, but preferably sequentially. For example, the method comprises steps (a) and (b), meaning that the method may comprise steps (a) and (b) performed sequentially, and may also comprise steps (b) and (a) performed sequentially. For example, reference to the process further comprising step (c) means that step (c) may be added to the process in any order, for example, the process may comprise steps (a), (b) and (c), may also comprise steps (a), (c) and (b), may also comprise steps (c), (a) and (b), etc.
In the present invention, the term "comprising" as used herein means either an open type or a closed type unless otherwise specified. For example, the term "comprising" may mean that other components not listed may also be included, or that only listed components may be included.
In the present invention, the term "modified activated carbon of a specific pH value" means activated carbon having a specific pH range obtained by treating a commercially available activated carbon raw material with an acidic reagent or an alkaline reagent, and particularly means activated carbon having a pH value of between 9 and 14 contained in the composite solid adsorbent of the present invention. For example, the modified activated carbon having a pH of 9 to 14 may indicate that the final pH of the activated carbon after the above treatment is between 9 and 14. Correspondingly, "raw activated carbon", "finished activated carbon" or "unmodified activated carbon" means activated carbon that has not been subjected to the above pH modification, and the specific pH value depends on the specific production process and production batch. However, it should be emphasized here that if the modification process according to the present invention is not performed, even if the original pH of the industrially produced activated carbon product is within the range of 9 to 14 as claimed in the present invention, it cannot be regarded as "modified" activated carbon, and is not used as "modified activated carbon having pH of 9 to 14" as described in the present invention. The applicant finds that the capability of removing 3-MCPD and GE impurities in grease can be influenced by the pH value of the modified activated carbon with the pH value of 9-14 whether the modified activated carbon is used as an adsorbent alone or mixed with nano materials to be used as the adsorbent, but the best grease purification effect can be realized when the modified activated carbon is mixed with the nano materials to form a composite type solid adsorbent.
According to a preferred embodiment of the present invention, the pH of the modified activated carbon may be within a range of any two of the following values: 9.0, 9.2, 9.4, 9.6, 9.8, 10.0, 10.2, 10.4, 10.6, 10.8, 11.0, 11.2, 11.4, 11.6, 11.8, 12.0, 12.2, 12.4, 12.6, 12.8, 13.0, 13.2, 13.4, 13.6, 13.8, 14.0.
According to a preferred embodiment of the present invention, the modification of the modified activated carbon may comprise the steps of: weighing certain mass of unmodified activated carbon or finished activated carbon, and mixing the finished activated carbon with alkaline aqueous solution or suspension such as CaO, Ca (OH)2、NaOH、KOH、Al2O3Mixing aqueous solution or water suspension of aluminum hydroxide, MgO, magnesium hydroxide, ammonia, lithium hydroxide, copper hydroxide, ferric hydroxide, ferrous hydroxide, copper hydroxide, carbonate, bicarbonate, etc., stirring at 30-150 deg.C, preferably 30-100 deg.C for 0.5-72 hr, preferably 24 hr, separating solid matter, washing with deionized water repeatedly, drying, pulverizing, sieving with 200 mesh sieveAnd obtaining the modified activated carbon with the pH value of 9-14. According to a preferred embodiment of the present invention, the modified activated carbon obtained by the above-mentioned repeated washing process is substantially free from residual metal ions derived from the alkali agent or solid precipitates containing metal ions. The modification treatment process only modifies the pH property of the activated carbon and does not deposit metal ion compounds such as aluminum, iron, copper, calcium and the like on the modified activated carbon.
The activated carbon of the present invention may have an appropriate specific surface area, porosity, and monomodal or multimodal pore size distribution as required. The diameter of the micropores of the activated carbon is less than 2nm, the diameter of the transition holes is 2-10nm, and the diameter of the macropores is 100-10000 nm. . The small pore volume is generally 0.15-0.90mL/g, and the transition pore area is generally 0.02-0.10 mL/g; the macropore volume is generally in the range from 0.2 to 0.5 mL/g. In a preferred embodiment of the present invention, the specific surface area of the activated carbon of the present invention measured by the BET method may be 2 to 3000 m2Per gram, preferably 10 to 2500 m2Per gram, more preferably 50-2000 m2A/g, more preferably 100-2A/g, more preferably 500-2A/g, more preferably 700-2Per gram.
The activated carbon of the present invention can be prepared by pyrolyzing and activating carbon-rich organic or inorganic materials, such as coal, wood, nut shells, coconut shells, walnut shells, apricot shells, date shells, rice hulls, petroleum products, waste materials, etc., through any physical or chemical process. The content of harmful impurities in the activated carbon should be sufficiently low so as not to cause contamination of the treated oil or fat. Commercially available activated carbon products meeting the above impurity requirements, after the above pH modification, can be used in the composite solid adsorbent of the present invention.
The nano material used in the present invention is selected from a nano carbon material, a nano metal material, or a mixture thereof. The shape of the nano carbon material is spherical, irregular granular, tubular or sheet, and the type of the nano carbon material is selected from one or more of the following types: fullerene, nano-diamond, carbon nano-tube, graphene and graphene oxide derivatives, reduced graphene oxide, graphene quantum dots and carbon dots. According to a preferred embodiment of the present invention, the nanocarbon material is preferably a single-walled, double-walled or multi-walled carbon nanotube having a diameter of 60nm or less, preferably graphene and derivatives thereof having a thickness of 10nm or less. According to a preferred embodiment of the present invention, the nanocarbon material is preferably a multiwall carbon nanotube, a single-wall carbon nanotube, or a multiwall carbon nanotube having a diameter of 60nm or less, and is preferably a graphene nanoplatelet having a thickness of 10nm or less.
According to a preferred embodiment of the present invention, the shape of the nanometal material is a nanometal particle or a nanometal cluster, the kind of which is selected from the group consisting of: silver, gold, copper, ruthenium, rhodium, palladium, osmium, iridium, platinum; silver alloy, gold alloy, copper alloy, ruthenium alloy, rhodium alloy, palladium alloy, osmium alloy, iridium alloy, platinum alloy; and an alloy formed by two or more of silver, gold, copper, ruthenium, rhodium, palladium, osmium, iridium and platinum; preferably selected from silver, silver alloys, gold and gold alloys. More preferably, the nano-metal material is a nano-scale silver particle, silver alloy particle, gold alloy particle, or gold-silver alloy particle. According to a preferred embodiment of the invention, the nano-metallic material is preferably a dispersible nano-copper powder.
In the composite solid adsorbent of the present invention, the modified activated carbon component and the nanomaterial are simply physically mixed without any close bonding such as hydrogen bonding, ionic bonding, covalent bonding, and coordinate bonding.
According to a preferred embodiment of the present invention, the weight ratio of the activated carbon to the nanomaterial contained in the adsorbent may be within a range of values formed by any two of the following ratios: 1:1, 1.5:1, 2:1, 5:1, 8:1, 10:1, 20:1, 30:1, 50:1, 70:1, 90:1, 100:1, 1000: 1.
The oil and fat which can be purified by the adsorbent of the invention comprises any vegetable oil and fat or structured fat containing adsorbable impurities, wherein the impurities preferably comprise chloropropanol ester and glycidyl ester, and can also comprise other common impurities in liquid oil and fat, and can be impurities introduced in an oil extraction raw material or common impurities introduced in an oil and fat processing process, such as trace free fatty acid, glycerol, peroxide, phospholipid, metal ions, microorganisms and the like. The vegetable oils and fats preferably include conventional oils and fats of vegetable origin as well as liquid synthetic oils and fats of mineral origin, non-limiting examples of which include peanut oil, soybean oil, linseed oil, castor oil, rapeseed oil, cottonseed oil, sesame oil, sunflower oil, palm oil, corn oil, olive oil, tea oil, walnut oil, canola oil, peppermint oil, coconut oil and the like, and also mixtures of the aforementioned oils and fats or mixtures of one or more of the aforementioned oils and any other oil. The structured fat refers to natural fat or fatty acid modified or reconstructed and has lipids meeting edible or medicinal nutritional requirements, and comprises MCT/MLCT, DAG oil, OPO lipid, CLA lipid and the like.
Examples
Preferred embodiments of the present invention are specifically exemplified in the following examples, but it should be understood that the scope of the present invention is not limited thereto. The raw material activated carbon, refined palm oil, carbon nanotubes and graphene nanoplatelet materials used in the following examples and comparative examples of the present invention are all commercially available.
Refined Palm Oil (RPO) was purchased from PGEO, malaysia;
the raw material active carbon is purchased from Shanghai Zhongji chemical import and export Limited company;
the carbon nanotubes, graphene nanoplatelets, and metal nanomaterials were purchased from Nanjing Xiancheng nanomaterial science and technology Co.
Experimental procedure for modification of activated carbon
In the following examples, industrial product activated carbon AC-N was modified by the steps described below, and the final pH of the modified activated carbon was adjusted by adjusting the amount of aqueous NaOH solution and the amount of washing water added.
The pH value detection method of the activated carbon refers to GB/T12496.7-1999 test method of wood activated carbon: measurement of pH value. preparation of modified activated carbon MAC-N1 with pH 8.56: taking 10g of finished active carbon AC-N (the AC-N active carbon is purchased from Shanghai Zhongji chemical industry import and export Co., Ltd., pH 6.54, and the proportion is shown in the tableArea 1400m2G, apparent density 370kg/m3. ) With 200 ml of 5% K2CO3Mixing the alkaline aqueous solution uniformly, stirring and reacting at 50 ℃ for 24 hours, and filtering to obtain activated carbon and K2CO3Separating the aqueous solution, repeatedly washing with deionized water, drying, pulverizing, sieving with 200 mesh sieve to obtain modified activated carbon MAC-N1, and detecting its pH value to be 8.56.
preparation of modified activated carbon MAC-N2 with pH 7.05: taking 10g of finished active carbon AC-N, and mixing with 100 ml of 5% Na2CO3Mixing the alkaline aqueous solution uniformly, stirring and reacting at 30 ℃ for 24h, and filtering to obtain activated carbon and Na2CO3Separating the aqueous solution, repeatedly washing with deionized water, drying, pulverizing, sieving with 200 mesh sieve to obtain modified activated carbon MAC-N2, and detecting its pH value to be 7.05.
preparing modified activated carbon MAC-N with pH value of 10.30: taking 10g of finished active carbon AC-N, uniformly mixing with 100 ml of 10% NaOH alkaline aqueous solution, stirring and reacting for 24h at 100 ℃, separating the active carbon from the NaOH aqueous solution by filtering, repeatedly washing with deionized water, drying, crushing, sieving with a 200-mesh sieve to obtain modified active carbon MAC-N, and detecting the pH value to be 10.30.
preparation of modified activated carbon MAC-J with pH 11.61: taking 10g of finished active carbon AC-J (AC-J active carbon is purchased from Shanghai Zhongji chemical industry import and export Co., Ltd., pH is 10.15, and specific surface area is 1000m2G, apparent density 310kg/m3. ) Mixing with 100 ml of 10% KOH alkaline aqueous solution, stirring and reacting for 24h at 100 ℃, separating the activated carbon from the KOH aqueous solution by filtering, repeatedly washing with deionized water, drying, crushing, sieving with a 200-mesh sieve to obtain modified activated carbon MAC-J, and detecting that the pH value is 11.61.
preparation of modified activated carbon MAC-N3 with pH 9.71: taking 10g of finished active carbon AC-N and 50 ml of NaHCO with the concentration of 10%3Mixing the alkaline aqueous solution uniformly, stirring and reacting at 50 ℃ for 24h, and filtering the mixture to obtain activated carbon and NaHCO3Separating the aqueous solution, repeatedly washing with deionized water, drying, pulverizing, sieving with 200 mesh sieve to obtain modified activated carbon MAC-N3, and detecting its pH value to be 9.71.
preparation of modified activated carbon MAC-N4 with pH 11.56: taking 10g of finished active carbon AC-N and 100 ml of 5 percent K2CO3Mixing the alkaline aqueous solution uniformly, stirring and reacting at 150 ℃ for 24 hours, and filtering to obtain activated carbon and K2CO3Separating the aqueous solution, repeatedly washing with deionized water, drying, pulverizing, sieving with 200 mesh sieve to obtain modified activated carbon MAC-N4, and detecting its pH value to be 11.56.
preparation of modified activated carbon MAC-N5 with pH 12.89: taking 10g of finished active carbon AC-N, uniformly mixing with 100 ml of 20% NaOH alkaline aqueous solution, stirring and reacting for 24h at 100 ℃, separating the active carbon from the NaOH aqueous solution by filtering, repeatedly washing with deionized water, drying, crushing, sieving with a 200-mesh sieve to obtain modified active carbon MAC-N5, and detecting the pH value to be 12.89.
Comparative example one: effect experiment for purifying refined palm oil by using modified activated carbon with pH of 9-14 as adsorbent
Two 200g portions of Refined Palm Oil (RPO) were taken, and 0.5% by weight (i.e., 1 g) and 3.5% by weight (i.e., 7 g) of modified activated carbon MAC-N (pH 10.30) based on the weight of the palm oil were added thereto, respectively, and heated to 180 ℃ with stirring under a nitrogen atmosphere, and treated at that temperature and under that condition for 120 minutes. After 120 minutes, the temperature is reduced to 60 ℃, and modified activated carbon MAC-N is removed by centrifugation to obtain a treated oil sample. The concentrations of the 3-MCPD ester, GE and Soap components in the oil sample before and after the adsorption treatment are summarized in the following table:
the quantitative analysis of 3-MCPD ester and GE used the detection method: indirect detection method DGF CVI18 (10); the method for detecting the Soap comprises the following steps: GB/T5533 and 2008 'determination of soap content in vegetable oil and fat by grain and oil inspection'.
Table 1: refining palm oil before and after adsorption with modified activated carbon MAC-N alone
| 3-MCPD ester (mg/kg) | GE(mg/kg) | Soap(ppm) | |
| Raw Material-RPO | 2.57 | 3.61 | 0 |
| 0.5% modified activated carbon MAC-N | 2.01 | 2.14 | 0 |
| 3.5% modified activated carbon MAC-N | 0.54 | 0.35 | 0 |
From the experimental results shown in table 1, it can be seen that the modified activated carbon with pH of 9-14 is used alone, and has a certain removal effect on both 3-MCPD ester and GE, when 0.5% of the addition amount is used, the GE removal rate is 40.72%, the 3-MCPD ester removal rate is only 21.79%, and as the addition amount of the activated carbon increases, the impurity removal effect is correspondingly improved; no influence on the soap content, namely no generation of redundant soap, and no influence on subsequent operation.
Comparative example two: effect experiment of purifying refined palm oil by using nano material as adsorbent alone
Five portions of 200g of Refined Palm Oil (RPO) were taken, and the nanomaterials (single-walled carbon nanotubes with a diameter of 1-2nm, multi-walled carbon nanotubes with a diameter of 20-30nm, multi-walled carbon nanotubes with a diameter of 50nm, graphene nanoplatelets with a thickness of 3-10nm, and dispersible copper nanoparticles with a diameter of 150-200 nm) shown in the following Table 2, which were 0.5% oil weight (i.e., 1 g) were added thereto, respectively, stirred and heated to 180 ℃ under the condition of introducing nitrogen gas, and treated at the temperature and under the condition for 120 minutes. After 120 minutes, the temperature is reduced to 60 ℃, and the nano material is removed by centrifugation to obtain a treated oil sample. The concentrations of the 3-MCPD ester, GE and Soap components in the oil sample before and after the adsorption treatment are summarized in the following table:
table 2: refining palm oil before and after adsorption with nanomaterial alone
From the experimental results shown in table 1 above, it can be seen that the above-mentioned contaminants cannot be effectively removed from palm oil by using the above-mentioned five carbon nanomaterials alone, but at the same time, the soap content is not increased.
Comparative example three: experiment of effect of purified palm oil by using modified activated carbon with pH of less than 9 alone as adsorbent
Two 200g portions of Refined Palm Oil (RPO) were taken, and 0.5% by weight (i.e., 1 g) of modified activated carbon having a pH value of less than 9 as shown in table 3 below was added thereto, respectively, based on the weight of the palm oil, heated to 180 ℃ with stirring under nitrogen gas, and treated at that temperature and condition for 120 minutes. After 120 minutes, the temperature is reduced to 60 ℃, and the modified activated carbon is removed by centrifugation to obtain a treated oil sample. The concentrations of the 3-MCPD ester, GE and Soap components in the oil sample before and after the adsorption treatment are summarized in the following table:
table 3: separately using refined palm oil before and after adsorption by modified activated carbon with pH value less than 9
| 3-MCPD ester (mg/kg) | GE(mg/kg) | Soap(mg/kg) | |
| Raw Material-RPO | 2.57 | 3.61 | 0 |
| 0.5% modified activated carbon MAC-N1 | 2.26 | 2.88 | 0 |
| 0.5% modified activated carbon MAC-N2 | 2.56 | 3.59 | 0 |
As can be seen from Table 3 above, the use of the two activated carbon materials, which have a pH of less than 9, alone, did not effectively remove the contaminants from palm oil, but did not result in an increase in soap content.
Comparative example four: effect experiment of purifying refined palm oil by using modified activated carbon with pH less than 9 and sodium hydroxide solution to adjust pH value to 9-14
Preparation of modified activated carbon MAC-N1-1: and (3) taking 10g of modified activated carbon MAC-N1 used in the third comparative example, drying at 80 ℃ for 2h, uniformly mixing the dried activated carbon with an alkaline aqueous solution of NaOH with the concentration of 5%, adjusting the addition of the NaOH to ensure that the pH value of the whole mixture is not washed by deionized water, directly drying, crushing, sieving by a 200-mesh sieve to obtain modified activated carbon MAC-N1-1, and detecting that the pH value is 10.30. 200g of Refined Palm Oil (RPO) was taken, and 0.5% by weight (i.e., 1 g) of modified activated carbon MAC-N1-1 was added thereto based on the weight of the palm oil, heated to 180 ℃ with stirring under a nitrogen atmosphere, and treated at that temperature and under that condition for 120 minutes. After 120 minutes, the temperature was reduced to 60 ℃ and the activated carbon was removed by centrifugation to give a treated oil sample. The concentrations of the 3-MCPD ester, GE and Soap components in the oil sample before and after the adsorption treatment are summarized in the following table:
table 4: experiment on purification effect of refined palm oil by using activated carbon with pH value less than 9 alone and using NaOH to adjust pH value
From the above table 4, it can be seen that if the activated carbon is not modified in the manner of the present invention to have a pH value between 9 and 14, but only modified activated carbon having a pH value outside the range of 9 to 14 is used, and the overall pH value is adjusted to a range of 9 to 14 by using a sodium hydroxide solution, under such conditions, the 3-MCPD ester is removed with a certain effect, but the effect is poor, the 3-MCPD ester removal rate is only 18.29%, and the GE content is rather increased. In addition, the soap content is greatly increased, the soap remained in the grease cannot be completely removed by simple filtration or centrifugation, and if the soap is not completely removed, the quality of the grease is directly influenced, and the characteristics of blackening the grease, having soap taste, reducing the stability and the like are reflected. The soap content in the grease can be reduced only by adding one-step washing or soap removal operation, and the loss and refining difficulty of the grease are increased. The reason for this is that sodium hydroxide is only distributed on the surface of the activated carbon by adjusting the pH value with a sodium hydroxide solution, and when the sodium hydroxide is adsorbed in the grease, the sodium hydroxide on the surface of the activated carbon preferentially reacts with free fatty acids in the grease to generate a large amount of soap, which makes the subsequent operation difficult.
Comparative example five: experiment on effect of purifying refined palm oil by using unmodified finished activated carbon alone as adsorbent
Two 200g portions of Refined Palm Oil (RPO) were taken, and 0.5% by weight (i.e. 1 g) of the oil of unmodified finished activated carbon AC-N (pH 6.54) and AC-J (pH 10.15) was added thereto, based on the weight of the palm oil, heated to 180 ℃ with stirring under nitrogen, and treated at that temperature and under that condition for 120 minutes. After 120 minutes, the temperature was reduced to 60 ℃ and the activated carbon was removed by centrifugation to give a treated oil sample. The concentrations of the 3-MCPD ester, GE and Soap components in the oil sample before and after the adsorption treatment are summarized in the following table:
table 5: palm oil before and after purification with unmodified finished activated carbon having a pH within or outside the range of 9-14 alone
| 3-MCPD ester (mg/kg) | GE(mg/kg) | Soap(ppm) | |
| Raw Material-RPO | 2.57 | 3.61 | 0 |
| 0.5 percent of finished product active carbon AC-N | 2.68 | 3.95 | 0 |
| 0.5 finished productActivated carbon AC-J | 3.08 | 4.19 | 0 |
As can be seen from the results in Table 5, if the finished activated carbon, which is not modified and has no pH value outside the range of 9 to 14, is directly used as the adsorbent, the contents of 3-MCPD ester and GE do not decrease or increase, and there is no effect of removing these impurity components. The reason is that the adsorption performance and the functional groups on the molecular surface of the finished product of the activated carbon are not changed through modification, and the finished product of the activated carbon has no effect on impurity components in grease.
Comparative example six: effect test Using an alkaline aqueous solution alone (pH 9-14)
200g of Refined Palm Oil (RPO) was taken, and 50 wt% NaOH aqueous solution was added thereto in an amount of 0.1 wt% based on the weight of the palm oil (i.e., 0.2 g), heated to 180 ℃ with stirring under a nitrogen gas atmosphere, and treated at that temperature and under that condition for 120 minutes. After 120 minutes the temperature was reduced to 60 ℃ and the solid material was removed by centrifugation to give a treated oil sample. The concentrations of the 3-MCPD ester, GE and Soap components in the oil sample before and after the adsorption treatment are summarized in the following table:
table 6: palm oil before and after treatment with an aqueous alkaline solution
| 3-MCPD ester (mg/kg) | GE(mg/kg) | Soap(mg/kg) | |
| Raw Material-RPO | 2.57 | 3.61 | 0 |
| 0.1% NaOH solution (50%) | 1.79 | 15.92 | 1035.80 |
As can be seen from the above table, in the case of using the alkaline aqueous solution alone, the 3-MCPD ester content in the palm oil is reduced, but GE is increased instead, the soap content is also increased greatly, and subsequent operations are necessary to reduce GE and the soap content, and subsequent refining increases the control difficulty and the oil loss.
The first embodiment is as follows: experiment on effect of modified activated carbon and graphene nanosheet composition with pH value within 9-14 serving as adsorbent in purifying refined palm oil
Four 200g portions of Refined Palm Oil (RPO) were taken, and a composition of MAC-N (pH 10.30) and graphene nanoplatelets in a weight ratio shown in the following table of 0.5% by weight of the oil (i.e., 1 g) was added thereto, respectively, based on the weight of the palm oil, stirred and heated to 180 ℃ under nitrogen gas, and treated at that temperature and condition for 120 minutes. After 120 minutes the temperature was reduced to 60 ℃ and the solid material was removed by centrifugation to give a treated oil sample. The concentrations of the 3-MCPD ester, GE and Soap components in the oil sample before and after the adsorption treatment are summarized in the following table:
table 7: refined palm oil before and after adsorption of compositions of MAC-N and graphene nanosheets in different proportions
| 3-MCPD ester (mg/kg) | GE(mg/kg) | Soap(ppm) | |
| Raw Material-RPO | 2.57 | 3.61 | 0 |
| MAC-N: graphene nanoplate 1:1 | 1.98 | 2.02 | 0 |
| MAC-N: graphene nanoplate 2:1 | 1.54 | 1.92 | 0 |
| MAC-N: graphene nanoplate 10:1 | 0.75 | 0.84 | 0 |
| MAC-N: graphene nanoplate 100:1 | 0.92 | 0.93 | 0 |
As can be seen from table 7 above, by contacting the grease with the composite adsorbent of the present invention, the content of both 3-MCPD ester and GE is significantly reduced, for example, when the ratio of MAC-N to graphene nanoplate is 10:1, the removal rate of 3-MCPD ester is 70.08%, which is improved by approximately 50% compared with the removal rate under the same addition amount of modified activated carbon, and the removal rate of GE is 76.73%, which is also improved by more than 30% compared with the removal rate under the same addition amount of modified activated carbon.
Example two: experiment on effect of modified activated carbon and multi-walled carbon nanotube composition with pH value within 9-14 serving as adsorbent in purification of refined palm oil
Four 200g portions of Refined Palm Oil (RPO) were taken, and a composition of MAC-J (pH 11.61) and multi-walled carbon nanotubes (20-30 nm long) in the weight ratio shown in the following table of 0.5% by weight of the oil (i.e., 1 g) was added thereto, respectively, to the weight of the palm oil, heated to 180 ℃ with stirring under nitrogen gas, and treated at that temperature and condition for 120 minutes. After 120 minutes the temperature was lowered to room temperature and the solid material was centrifuged off to give a treated oil sample. The concentrations of the 3-MCPD ester, GE and Soap components in the oil sample before and after the adsorption treatment are summarized in the following table:
table 8: refined palm oil before and after adsorption of compositions of MAC-J and multi-walled carbon nanotubes in different proportions
From the above table 8, it can be seen that, by contacting the grease with the composite adsorbent of the present invention, the content of both 3-MCPD ester and GE is significantly reduced, and the best effect is that the removal rate of 3-MCPD ester is 94.16%, which is more than 70% higher than the removal rate of the same amount of modified activated carbon, and the GE removal rate is higher.
Example three: experiment on effect of composition of modified activated carbon with pH value within 9-14 and dispersible nano-copper powder with diameter of 150-200nm serving as adsorbent in purification of refined palm oil
Four 200g portions of Refined Palm Oil (RPO) were taken and added to each of the compositions of MAC-N3(pH 9.71) and the 200nm diameter dispersible copper nanopowder at a weight ratio indicated in the table below of 0.5% oil weight (i.e., 1 g) based on the weight of the palm oil. The temperature was raised to 160 ℃ under vacuum (5 mbar) with stirring and the treatment was carried out for 180 minutes at this temperature and under these conditions. After 180 minutes the temperature was reduced to 60 ℃ and the solid material was removed by centrifugation to give a treated oil sample. The concentrations of the 3-MCPD ester, GE and Soap components in the oil sample before and after the adsorption treatment are summarized in the following table:
table 9: refined palm oil before and after adsorption of modified activated carbon and dispersible copper nanoparticle powder compositions with different pH values
From the above table 9, it can be seen that there is a significant reduction effect on both the 3-MCPD ester and GE contents by contacting the grease with the above-mentioned composite adsorbent of the present invention. And no soap is generated after treatment, and the subsequent operation is not influenced.
Example four: effect experiment of using modified activated carbon with different pH values and graphene nanosheet with thickness of 3-10nm as adsorbent for purifying refined palm oil
Four portions of 200g of Refined Palm Oil (RPO) were taken, and a composition of pH modified activated carbon and graphene nanoplatelets having a thickness of 3-10nm as shown in the following table was added thereto at 0.5% oil weight (i.e., 1 g), respectively, based on the weight of the palm oil, wherein the weight ratio of the modified activated carbon to the graphene nanoplatelets having a thickness of 3-10nm was 10: 1. The temperature was raised to 180 ℃ with stirring and heating under nitrogen, and the treatment was carried out at this temperature and under these conditions for 120 minutes. After 120 minutes the temperature was reduced to 60 ℃ and the solid material was removed by centrifugation to give a treated oil sample. The concentrations of the 3-MCPD ester, GE and Soap components in the oil sample before and after the adsorption treatment are summarized in the following table:
table 10: refined palm oil before and after adsorption of modified activated carbon and graphene nanosheet composition with different pH values
| 3-MCPD ester (mg/kg) | GE(mg/kg) | Soap(ppm) | |
| Raw Material-RPO | 2.57 | 3.61 | 0 |
| MAC-N1(pH＝8.56) | 1.62 | 2.03 | 0 |
| MAC-N3(pH＝9.71) | 0.80 | 0.93 | 0 |
| MAC-N(pH＝10.30) | 0.75 | 0.84 | 0 |
| MAC-N4(pH＝11.56) | 0.69 | 0.79 | 0 |
| MAC-N5(pH＝12.89) | 0.71 | 0.80 | 0 |
From the above table 10, it can be seen that the oil and fat are contacted with the composite adsorbent of the present invention, so that the contents of 3-MCPD ester and GE are significantly reduced under different pH conditions of the activated carbon. And no soap is generated after treatment, and the subsequent operation is not influenced.
Example five: experiment on effect of MAC-N (pH 10.30) and single-walled carbon nanotube with diameter of 1-2nm on purification of refined palm oil by using composition as adsorbent
Four portions of 200g of Refined Palm Oil (RPO) are taken, and a certain amount of modified activated carbon MAC-N (pH value is 10.30) and a composition of single-wall carbon nanotubes with the diameter of 1-2nm are respectively added into the refined palm oil, wherein the weight ratio of the modified activated carbon to the single-wall carbon nanotubes with the diameter of 1-2nm is 10: 1. The mixture is heated while stirring under vacuum (1 mbar) and treated at this temperature and for a period of time. Then the temperature is reduced to 60 ℃, and solid matters are removed by centrifugation, thus obtaining the treated oil sample. The concentrations of the 3-MCPD ester, GE and Soap components in the oil sample before and after the adsorption treatment are summarized in the following table:
table 11: refined palm oil before and after adsorption of a composition of MAC-N (pH 10.30) and single-walled carbon nanotubes having a diameter of 1-2nm
From the above table 11, it can be seen that the oil and fat are contacted with the composite adsorbent of the present invention under different conditions, and the content of 3-MCPD ester and GE are both significantly reduced. And no soap is generated after treatment, and the subsequent operation is not influenced.
Claims (10)
1. A composite solid adsorbent, comprising:
(i) activated carbon; and
(ii) a nanomaterial;
the activated carbon has a pH of 9 to 14, preferably 9.1 to 13.
2. The composite solid adsorbent according to claim 1, wherein the weight ratio of the activated carbon to the nanomaterial is 1:1 to 1000:1, preferably 1:1 to 100:1, and more preferably 2:1 to 100: 1.
3. The composite solid adsorbent of claim 1, wherein the activated carbon is an activated carbon modified by: an unmodified raw activated carbon is provided, which is treated with an alkaline agent to obtain a modified activated carbon having a pH of 9 to 14, preferably 9.1 to 13, more preferably 9.5 to 13.
4. The composite solid adsorbent according to claim 3, wherein the treatment of the raw activated carbon with the alkaline agent comprises the steps of:
a. treating the raw material active carbon by using an alkaline reagent;
b. separating the alkaline reagent from the treated raw material active carbon;
c. washing the treated raw activated carbon to obtain activated carbon with a pH value of 9-14, preferably 9.1-13, more preferably 9.5-13, preferably drying the treated raw activated carbon, further preferably crushing the treated dried raw activated carbon, further preferably sieving the treated dried crushed raw activated carbon, wherein the sieving is preferably performed by using a sieve with 50-800 meshes, preferably using a sieve with 150-400 meshes, and further preferably using a sieve with 200-250 meshes;
the alkaline agent is selected from aqueous solutions or suspensions in water of the following compounds: CaO, Ca (OH)2、NaOH、KOH、Al2O3Aluminum hydroxide, MgO, magnesium hydroxide, ammonia, lithium hydroxide, copper hydroxide, ferric hydroxide, ferrous hydroxide, cupric hydroxide, carbonAcid salts, bicarbonate salts, and combinations of two or more thereof;
step c uses water for washing.
5. The composite solid adsorbent of claim 1, wherein the nanomaterial is selected from a nanocarbon material, a nanometal material, or a mixture thereof.
6. The composite solid adsorbent according to claim 5, wherein the shape of the nanocarbon material is spherical, irregular granular, tubular or sheet, and the type thereof is selected from one or more of the following: fullerene, nano-diamond, carbon nano-tube, graphene and graphene oxide, reduced graphene oxide, graphene quantum dot and carbon dot which are derivatives of graphene; single-walled, double-walled or multi-walled carbon nanotubes with a diameter of less than 60nm are preferred, and graphene and derivatives thereof with a thickness of less than 10nm are preferred;
the shape of the nano metal material is nano metal particles or nano metal clusters, and the types of the nano metal particles or nano metal clusters are selected from the following groups: silver, gold, copper, ruthenium, rhodium, palladium, osmium, iridium, platinum, alloys of the above elements, and alloys of two or more of the above elements with each other; preferably selected from copper, silver alloys, gold and gold alloys.
7. A method for purifying fats and oils, the method comprising:
mixing the composite solid adsorbent according to any one of claims 1 to 6 with a fat or oil containing impurities so that the adsorbent adsorbs at least a part of the impurities;
separating the adsorbent having adsorbed at least a portion of the impurities from the fat.
8. The method of claim 7, comprising at least one of the following features:
1) the amount of the adsorbent is 0.1 to 20% by weight, preferably 0.1 to 10% by weight, more preferably 0.1 to 5% by weight, and still more preferably 0.1 to 3.5% by weight, based on the total weight of the oil or fat;
2) the adsorbent is mixed with the grease containing impurities at the temperature of 150 ℃ to 250 ℃, preferably 160 ℃ to 230 ℃;
3) mixing the adsorbent with the oil containing impurities for at least 30 minutes, preferably 60-180 minutes;
4) mixing the adsorbent with oil containing impurities, and adjusting the temperature to be below 80 ℃; and
5) separating the adsorbent having adsorbed at least a portion of the impurities from the oil or fat by filtration or centrifugation.
9. The process of claim 7 wherein the impurities comprise one or both of chloropropanol esters and glycidyl esters, and preferably the fat does not undergo significant saponification to yield soap species of no more than 100ppm throughout the process; preferably, no saponification reaction occurs and no soap is formed.
10. Grease obtained after purification by the method according to any one of claims 7 to 9, preferably the sum of the contents of chloropropanol ester and glycidyl ester in the grease is less than 5ppm, preferably less than 3ppm, and more preferably less than 1 ppm.
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| WO2023187628A3 (en) * | 2022-03-31 | 2023-12-07 | Technoilogy S.R.L. | Process for removing organic chlorine from used cooking oils (uco), animal and vegetable recovery fats (avr), and pyrolysis oils (po) derived from waste |
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