CN115178240A - Plasticizer for removing phthalate esters in camellia oleosa seed oil, preparation method and use method thereof - Google Patents
Plasticizer for removing phthalate esters in camellia oleosa seed oil, preparation method and use method thereof Download PDFInfo
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- CN115178240A CN115178240A CN202210873583.3A CN202210873583A CN115178240A CN 115178240 A CN115178240 A CN 115178240A CN 202210873583 A CN202210873583 A CN 202210873583A CN 115178240 A CN115178240 A CN 115178240A
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- 235000015112 vegetable and seed oil Nutrition 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims abstract description 42
- 235000005593 Camellia sinensis f parvifolia Nutrition 0.000 title claims abstract description 31
- 244000041840 Camellia sinensis f. parvifolia Species 0.000 title claims abstract description 31
- 239000004014 plasticizer Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 title description 4
- 239000003463 adsorbent Substances 0.000 claims abstract description 83
- 235000018597 common camellia Nutrition 0.000 claims abstract description 49
- 238000001179 sorption measurement Methods 0.000 claims abstract description 47
- 239000008029 phthalate plasticizer Substances 0.000 claims abstract description 28
- 238000000197 pyrolysis Methods 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 21
- 235000019198 oils Nutrition 0.000 claims abstract description 17
- 241001122767 Theaceae Species 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 230000003213 activating effect Effects 0.000 claims abstract description 10
- 230000004913 activation Effects 0.000 claims abstract description 10
- 239000012535 impurity Substances 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000011084 recovery Methods 0.000 claims abstract description 5
- 240000001548 Camellia japonica Species 0.000 claims description 48
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 38
- 238000002791 soaking Methods 0.000 claims description 22
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 19
- 239000011148 porous material Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000012190 activator Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 238000012545 processing Methods 0.000 abstract description 6
- 241000209507 Camellia Species 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 41
- 239000003921 oil Substances 0.000 description 15
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 7
- -1 appliances Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000008158 vegetable oil Substances 0.000 description 4
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 3
- 239000010495 camellia oil Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 2
- 239000000796 flavoring agent Substances 0.000 description 2
- 235000019634 flavors Nutrition 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- YYGNTYWPHWGJRM-UHFFFAOYSA-N (6E,10E,14E,18E)-2,6,10,15,19,23-hexamethyltetracosa-2,6,10,14,18,22-hexaene Chemical compound CC(C)=CCCC(C)=CCCC(C)=CCCC=C(C)CCC=C(C)CCC=C(C)C YYGNTYWPHWGJRM-UHFFFAOYSA-N 0.000 description 1
- 241000526900 Camellia oleifera Species 0.000 description 1
- 240000007817 Olea europaea Species 0.000 description 1
- BHEOSNUKNHRBNM-UHFFFAOYSA-N Tetramethylsqualene Natural products CC(=C)C(C)CCC(=C)C(C)CCC(C)=CCCC=C(C)CCC(C)C(=C)CCC(C)C(C)=C BHEOSNUKNHRBNM-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 229930003427 Vitamin E Natural products 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- PRAKJMSDJKAYCZ-UHFFFAOYSA-N dodecahydrosqualene Natural products CC(C)CCCC(C)CCCC(C)CCCCC(C)CCCC(C)CCCC(C)C PRAKJMSDJKAYCZ-UHFFFAOYSA-N 0.000 description 1
- 239000008157 edible vegetable oil Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229940031439 squalene Drugs 0.000 description 1
- TUHBEKDERLKLEC-UHFFFAOYSA-N squalene Natural products CC(=CCCC(=CCCC(=CCCC=C(/C)CCC=C(/C)CC=C(C)C)C)C)C TUHBEKDERLKLEC-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229930003799 tocopherol Natural products 0.000 description 1
- 229960001295 tocopherol Drugs 0.000 description 1
- 239000011732 tocopherol Substances 0.000 description 1
- 235000010384 tocopherol Nutrition 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 description 1
Classifications
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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
-
- 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28066—Surface area, e.g. B.E.T specific surface area being more than 1000 m2/g
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
- C10B53/02—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
-
- 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
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
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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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
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- Chemical Kinetics & Catalysis (AREA)
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- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Microbiology (AREA)
- Wood Science & Technology (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a method for removing phthalate plasticizer in camellia seed oil, a preparation method and a use method thereof. The adsorption mainly comprises the following steps: (1) preparing an adsorbent: oil tea shell → impurity removal → activation → pyrolysis → recovery of activating agent → drying → refinement → finished product; (2) Removing a phthalate plasticizer in the camellia oleosa seed oil: the camellia oleosa seed oil polluted by the phthalate plasticizer → adsorption by adding an adsorbent → filtration → purified camellia oleosa seed oil. The adsorbent takes the processing residues as raw materials, has simple and convenient preparation process, high plasticizer removal rate, lower processing cost and environmental cost, simple adsorption operation and wide popularization and application.
Description
Technical Field
The invention relates to the technical field of deep processing of camellia seed oil, in particular to a plasticizer for removing phthalate esters in camellia seed oil, a preparation method and a use method thereof.
Background
The camellia seed oil (also known as camellia seed oil, tea oil and camellia oil) is rich in vitamin E, phytosterol and other nutrient components due to the content of unsaturated fatty acid of the camellia seed oil (more than 85 percent), and has the reputation of 'first oriental oil' and 'olive oriental oil'. The phthalate plasticizer is widely applied to plastic products as an additive for improving the plasticity and strength of plastics, is connected with a plastic matrix by hydrogen bonds or Van der Waals force, is soluble in most organic solvents and oil, and is very easy to migrate to oil-tea camellia seed oil products from links using the plastic products, such as raw material packing materials, appliances, product packing materials and the like, in the oil-tea camellia seed oil processing process. At present, the technology for removing the phthalate plasticizer, which can realize large-scale production, mainly comprises adsorption removal and high vacuum-high temperature removal. Chinese patent document CN110655977A discloses a method for removing a plasticizer in edible oil. PAEs (phthalic acid esters) are usually removed under the high vacuum condition, the system temperature is higher than 200 ℃, on one hand, the inherent components of the vegetable oil can generate irreversible reaction under the high temperature condition, such as flavor substances, pigments and the like; on the other hand, the loss of heat-sensitive active ingredients such as tocopherol, phytosterol, squalene and the like in the vegetable oil is extremely large under the high-temperature condition. The adsorption removal of PAEs can not damage the inherent components and the thermosensitive effective components of the vegetable oil, and is more suitable for areas with extremely high requirements on the original fragrance of the vegetable oil, particularly two broad areas. From the existing research results, it is known that the conventional decolorization adsorbent is ineffective on PAEs, while some special adsorbents have obvious effect on removing PAEs, and whether the adsorption effect changes with the changes of temperature, pH and the like of a mixed system or not is still to be examined. The phthalate plasticizer has high boiling point and stable molecular structure, and the disclosed removal conditions are severe, so that the nutritional ingredients and flavor of the camellia seed oil are greatly influenced, special equipment is required to be input, and the removal cost is high.
Disclosure of Invention
After the adsorbent and the using method are used for treatment, the phthalate removal rate in the camellia seed oil reaches over 80 percent and meets the limit value of the national health department, namely, the di (2-ethyl) hexyl phthalate (DEHP) is less than or equal to 1.5mg/kg, the di-n-butyl phthalate (DBP) is less than or equal to 0.3mg/kg, and the diisononyl phthalate (DINP) is less than or equal to 9.0mg/kg, so that the adsorbent has a good effect.
The technical scheme of the invention is as follows:
a preparation method of an adsorbent for removing phthalate plasticizers in camellia oleosa seed oil comprises the following steps: oil tea shell → impurity removal → activation → pyrolysis → recovery of activating agent → drying → refinement → finished product.
Further, the activating agent used for activation is phosphoric acid, the dosage of the activating agent is 2.5-4 times of the weight of the oil-tea camellia shells, and the activating method comprises the steps of soaking for 10-12 hours at room temperature, and then drying for 20-24 hours at the temperature of 98-103 ℃.
Further, the pyrolysis method comprises the steps of heating the raw materials to 650-750 ℃ at the initial temperature of 68-72 ℃ at the heating rate of 4-5 ℃/min, keeping the temperature for 110-130min, and keeping the pyrolysis atmosphere in a hydrogen atmosphere.
Further, the activator recovery method comprises washing with deionized water to pH 5.4-5.6, and drying at 97-105 deg.C to water content of less than 10%.
Further, the refining method is to select 100-200 meshes of products after crushing by a crusher
The invention also provides an adsorbent for removing the phthalate plasticizer in the camellia seed oil, and the surface area of the adsorbent is more than 1650m 2 The pore diameter is between 4.0nm and 4.5nm.
The invention also provides a use method of the adsorbent for removing the phthalate plasticizer in the camellia oleosa seed oil, which comprises the following steps: camellia seed oil contaminated with phthalate plasticizers → adsorption with adsorbent → filtration → purified camellia seed oil.
Further, the adsorbent is added according to the weight of 0.2-0.5% of the camellia oleosa seed oil.
Further, adsorbing for 1.5-2.5h at room temperature by using the adsorbent.
Further, 0.08-0.12 wt% of diatomite is added into the camellia seed oil, and the mixture is filtered after being uniformly stirred.
The invention has the technical principle and beneficial effects of removing the phthalate in the oil tea seed oil:
(1) The phthalate plasticizer has high boiling point and stable property, and most of the phthalate plasticizer is insoluble or slightly soluble in water. By adjusting the process parameters such as the proportion of the activating agent to the raw materials, the activation temperature and the like, the pore size and the surface groups of the adsorbent are directionally regulated and controlled, so that the plasticizer molecules can be more stably coated.
(2) The total pore area of more than 1650m can be obtained by adopting the process of the invention 2 The removal rate of the adsorbent with the pore diameter of 4.0-4.5 nm to the phthalate plasticizer in the camellia oleosa seed oil reaches more than 80%, the loss rate of the camellia oleosa seed oil is less than 10%, and the color change is small, which shows that the process of the invention has good technical effect and can be widely popularized and applied.
(3) The method takes Guangxi forestry processing residues as raw materials, and prepares the special adsorbent according to the molecular structure of the phthalate plasticizer, so that the added value of the processing industry of forest products in a region can be improved, and a solid theoretical basis can be laid for guaranteeing national grain and oil safety and assisting the healthy development of Guangxi special oil.
The specific implementation mode is as follows:
the invention is further described with reference to specific examples, without limiting the scope of protection and the scope of application of the invention.
Example 1
A use method of an adsorbent for removing phthalate plasticizers in camellia oleosa seed oil comprises the following steps:
(1) Preparing an adsorbent: removing impurities from oil tea hulls, adding 2.5 times of phosphoric acid by weight, soaking at room temperature for 10h, drying at 100 ℃ for 20h, performing pyrolysis at 70 ℃ under hydrogen atmosphere, heating to 650 ℃ at 5 ℃/min, keeping for 120min, washing with deionized water to pH5.5, drying at 100 ℃ until the water content is less than 10%, and crushing to obtain the finished adsorbent.
(2) Removing a phthalate plasticizer in the camellia oleosa seed oil: and (2) adding the 100-200-mesh adsorbent in the step (1) according to 0.2% of the weight of the camellia seed oil, adsorbing for 2 hours at room temperature, adding diatomite of which the weight is 0.1% of the weight of the camellia seed oil, uniformly stirring, and filtering.
The quality indexes of the oil-tea camellia seed oil before and after adsorption, the pore area and the pore diameter of the adsorbent and the adsorption effect are detected, and the experimental results are shown in the following table:
example 2
A use method of an adsorbent for removing phthalate plasticizers from camellia oleosa seed oil comprises the following steps:
(1) Preparing an adsorbent: removing impurities from oil tea shells, adding 3.0 times of phosphoric acid, soaking at room temperature for 10h, drying at 100 ℃ for 21h, performing pyrolysis at an initial temperature of 70 ℃ in a hydrogen atmosphere, heating to 700 ℃ at a speed of 5 ℃/min, keeping for 120min, washing with deionized water to a pH of 5.5, drying at 100 ℃ until the water content is less than 10%, and crushing to obtain the finished adsorbent.
(2) Removing a phthalate plasticizer in the camellia oleosa seed oil: and (2) adding the 100-200-mesh adsorbent in the step (1) according to 0.3% of the weight of the camellia seed oil, adsorbing for 2 hours at room temperature, adding diatomite of which the weight is 0.1% of the weight of the camellia seed oil, uniformly stirring, and filtering.
The quality indexes of the oil-tea camellia seed oil before and after adsorption, the pore area and the pore diameter of the adsorbent and the adsorption effect are detected, and the experimental results are shown in the following table:
example 3
A use method of an adsorbent for removing phthalate plasticizers in camellia oleosa seed oil comprises the following steps:
(1) Preparing an adsorbent: removing impurities from oil tea shells, adding 3.5 times of phosphoric acid, soaking at room temperature for 11h, drying at 100 ℃ for 22h, performing pyrolysis at an initial temperature of 70 ℃ in a hydrogen atmosphere, increasing the temperature to 750 ℃ at a speed of 5 ℃/min, keeping the temperature for 120min, washing with deionized water to pH5.5, drying at 100 ℃ until the water content is less than 10%, and crushing to obtain the finished adsorbent.
(2) Removing the phthalate plasticizer in the camellia oleosa seed oil: and (2) adding the 100-200-mesh adsorbent in the step (1) according to 0.4% of the weight of the camellia seed oil, adsorbing for 2 hours at room temperature, adding diatomite of which the weight is 0.1% of the weight of the camellia seed oil, uniformly stirring, and filtering.
The quality indexes of the oil-tea camellia seed oil before and after adsorption, the pore area and the pore diameter of the adsorbent and the adsorption effect are detected, and the experimental results are shown in the following table:
example 4
A use method of an adsorbent for removing phthalate plasticizers in camellia oleosa seed oil comprises the following steps:
(1) Preparing an adsorbent: removing impurities from oil tea shells, adding 4.0 times of phosphoric acid, soaking at room temperature for 12h, drying at 100 ℃ for 24h, performing pyrolysis at an initial temperature of 70 ℃ in a hydrogen atmosphere, increasing the temperature to 750 ℃ at a speed of 5 ℃/min, keeping the temperature for 120min, washing with deionized water to a pH value of 5.5, drying at 100 ℃ until the water content is less than 10%, and crushing to obtain the finished adsorbent.
(2) Removing the phthalate plasticizer in the camellia oleosa seed oil: and (2) adding the 100-200-mesh adsorbent in the step (1) according to 0.5% of the weight of the camellia seed oil, adsorbing for 2 hours at room temperature, adding diatomite of which the weight is 0.1% of the weight of the camellia seed oil, uniformly stirring, and filtering.
The quality indexes of the oil-tea camellia seed oil before and after adsorption, the pore area and the pore diameter of the adsorbent and the adsorption effect are detected, and the experimental results are shown in the following table:
example 5
A use method of an adsorbent for removing phthalate plasticizers from camellia oleosa seed oil comprises the following steps:
(1) Preparing an adsorbent: removing impurities from oil tea hulls, adding 2.5 times of phosphoric acid by weight, soaking at room temperature for 12h, drying at 100 ℃ for 24h, performing pyrolysis at 70 ℃ under hydrogen atmosphere, heating to 750 ℃ at 5 ℃/min, keeping for 120min, washing with deionized water to pH5.5, drying at 100 ℃ until the water content is less than 10%, and crushing to obtain the finished adsorbent.
(2) Removing a phthalate plasticizer in the camellia oleosa seed oil: and (2) adding the 100-200-mesh adsorbent in the step (1) according to 0.2% of the weight of the camellia seed oil, adsorbing for 2 hours at room temperature, adding diatomite of which the weight is 0.1% of the weight of the camellia seed oil, uniformly stirring, and filtering.
The quality indexes of the oil-tea camellia seed oil before and after adsorption, the pore area and the pore diameter of the adsorbent and the adsorption effect are detected, and the experimental results are shown in the following table:
example 6
A use method of an adsorbent for removing phthalate plasticizers in camellia oleosa seed oil comprises the following steps:
(1) Preparing an adsorbent: removing impurities from oil tea hulls, adding 4.0 times of phosphoric acid by weight, soaking at room temperature for 10h, drying at 100 ℃ for 22h, performing pyrolysis at 70 ℃ under hydrogen atmosphere, heating to 700 ℃ at 5 ℃/min, keeping for 120min, washing with deionized water to pH5.5, drying at 100 ℃ until the water content is less than 10%, and crushing to obtain the finished adsorbent.
(2) Removing a phthalate plasticizer in the camellia oleosa seed oil: and (2) adding the 100-200-mesh adsorbent in the step (1) according to 0.3% of the weight of the camellia seed oil, adsorbing for 2 hours at room temperature, adding diatomite of which the weight is 0.1% of the weight of the camellia seed oil, uniformly stirring, and filtering.
The quality indexes of the oil-tea camellia seed oil before and after adsorption, the pore area and the pore diameter of the adsorbent and the adsorption effect are detected, and the experimental results are shown in the following table:
research on influence of process parameters on adsorption effect
(I) influence of different phosphoric acid dosage on adsorption effect
Basically the same as the process of example 1, the amount of phosphoric acid added is controlled to be 2 times, 3 times, 3.5 times, 4 times and 4.5 times of the weight of the camellia oleifera shells, and comparative example 1, comparative example 2, comparative example 3, comparative example 4 and comparative example 5 are respectively noted. The plasticizer adsorption effects of example 1 and comparative examples 1 to 5 were examined, as shown in the following table.
From the above table, it can be seen that: the adsorption effect is affected differently by different phosphoric acid addition amounts, when the phosphoric acid addition amount is controlled to be less than 3 times of the weight of the oil tea shell, the adsorption effect is better and better, and the phosphoric acid activation effect is better and better; when the adding amount of the phosphoric acid is controlled to be 3 times of the weight of the oil-tea camellia shells, the DEHP removal rate, the DBP removal rate and the DINP removal rate are optimal, and when the adding amount of the phosphoric acid is controlled to be more than 3 times of the weight of the oil-tea camellia shells, the adsorption effect is increasingly poor, the increase of the phosphoric acid amount is unfavorable for the activation effect, so that the adding amount of the phosphoric acid is the optimal amount when the adding amount of the phosphoric acid is controlled to be 3 times of the weight of the oil-tea camellia shells, and the adsorption effect is the best.
(II) influence of different pyrolysis temperatures on adsorption Effect
The process was substantially the same as that of example 2, and the pyrolysis temperatures were controlled at 500 ℃, 550 ℃, 600 ℃, 650 ℃, and 750 ℃, and comparative examples 6, 7, 8, 9, and 10 were respectively described. The plasticizer removal rates of example 2 and comparative examples 6-10 are shown in the table below.
From the above table, it can be seen that: different pyrolysis temperatures have different influences on the adsorption effect, and when the pyrolysis temperature is lower than 700 ℃, the adsorption effect is better and better along with the rise of the temperature; when the pyrolysis temperature is 700 ℃, the DEHP removal rate, the DBP removal rate and the DINP removal rate are optimal, and when the pyrolysis temperature is higher than 700 ℃, the adsorption effect is increasingly poor, which indicates that the increase of the pyrolysis temperature is not beneficial to the adsorption effect, so that the optimal pyrolysis temperature is obtained when the pyrolysis temperature is controlled to be 700 ℃, and the adsorption effect is the best.
(III) influence of different adsorbent addition amounts on adsorption effects
Substantially the same as the process of example 3, the added adsorbent was controlled to be 0.1%, 0.2%, 0.3%, 0.5%, 0.6% by weight, and comparative examples 11, 12, 13, 14, and 15 were used. The plasticizer removal rates of example 3 and comparative examples 11-15 are shown in the following table.
From the above table it can be seen that: the adsorption effect is affected differently by the addition amount of different adsorbents, and when the weight of the added adsorbent is less than 0.4%, the comprehensive adsorption effect is better and better along with the increase of the weight of the added adsorbent; when the weight of the added adsorbent is 0.4%, the comprehensive DEHP removal rate, DBP removal rate and DINP removal rate are optimal, and when the weight of the added adsorbent is more than 0.4%, the adsorption effect is increasingly poor, which indicates that the increase of the weight of the adsorbent is not beneficial to the adsorption effect, so that the addition amount of the adsorbent is optimal when the weight of the added adsorbent is controlled to be 0.4%, the adsorption effect is the best, and therefore, the optimal addition amount of the adsorbent is controlled, and the production cost is favorably saved.
(IV) influence of different soaking time on adsorption effect
The process is basically the same as that of example 6, the soaking time is controlled to be 8h, 9h, 11h, 12h and 13h, and comparative examples 16, 17, 18, 19 and 20 are recorded. The plasticizer removal rates of example 6 and comparative examples 16-20 are shown in the table below.
From the above table it can be seen that: different soaking times have different influences on the adsorption effect, when the soaking time is less than 11h, the comprehensive adsorption effect is better and better along with the increase of the soaking time, and the longer the soaking time of the adsorbent is, the better the activation effect is; when the soaking time is 11 hours, the comprehensive DEHP removal rate, DBP removal rate and DINP removal rate reach the best, which indicates that the soaking activation is best at the moment; when the soaking time is longer than 11h, the adsorption effect is worse, which indicates that the increase of the soaking time is not beneficial to the adsorption effect, so that the best soaking time is obtained when the soaking time is controlled to be 11h, the adsorption effect is best, and if the best soaking time is not controlled, the time is greatly wasted, and the best adsorption effect cannot be obtained.
Example 7
A use method of an adsorbent for removing phthalate plasticizers in camellia oleosa seed oil comprises the following steps:
(3) Preparing an adsorbent: removing impurities from oil tea shells, adding 3 times of phosphoric acid, soaking at room temperature for 11h, drying at 100 ℃ for 22h, performing pyrolysis at an initial temperature of 70 ℃ in a hydrogen atmosphere, increasing the temperature to 700 ℃ at a speed of 5 ℃/min, keeping the temperature for 120min, washing with deionized water to a pH value of 5.5, drying at 100 ℃ until the water content is less than 10%, and crushing to obtain the finished adsorbent.
(4) Removing a phthalate plasticizer in the camellia oleosa seed oil: and (2) adding the 100-200-mesh adsorbent in the step (1) according to 0.4% of the weight of the camellia seed oil, adsorbing for 2 hours at room temperature, adding diatomite of which the weight is 0.1% of the weight of the camellia seed oil, uniformly stirring, and filtering.
The adsorption effect is detected, and the experimental results are shown in the following table:
in conclusion, the total pore area of more than 1650m can be obtained by adopting the process of the invention 2 The removal rate of the adsorbent with the pore diameter of 4.0-4.5 nm to the phthalate plasticizer in the camellia oleosa seed oil reaches more than 80%, the loss rate of the camellia oleosa seed oil is less than 10%, and the color change is small, wherein the removal rate of DEHP obtained in example 7 under the screened process parameters is 83.16%, the removal rate of DBP is 83.78%, and the removal rate of DINP is 82.26%, which shows that the process of the invention has good technical effect and can be widely popularized and applied.
Claims (10)
1. A preparation method of an adsorbent for removing phthalate plasticizers from camellia oleosa seed oil is characterized by comprising the following steps: oil tea shell → impurity removal → activation → pyrolysis → recovery of activating agent → drying → refinement → finished product.
2. The preparation method of the adsorbent for removing the phthalate plasticizer in the camellia oleosa seed oil according to claim 1, wherein the method comprises the following steps: the activating agent used for activation is phosphoric acid, the dosage of the activating agent is 2.5-4 times of the weight of the oil-tea camellia shells, the activating method comprises the steps of soaking for 10-12 hours at room temperature, and then drying for 20-24 hours at the temperature of 98-103 ℃.
3. The preparation method of the adsorbent for removing the phthalate plasticizer from the camellia seed oil according to claim 1, wherein the adsorbent comprises the following components: the pyrolysis method comprises heating at an initial temperature of 68-72 deg.C and a heating rate of 4-5 deg.C/min to 650-750 deg.C, maintaining for 110-130min, and the pyrolysis atmosphere is hydrogen atmosphere.
4. The preparation method of the adsorbent for removing the phthalate plasticizer from the camellia seed oil according to claim 1, wherein the adsorbent comprises the following components: the activator recovery method comprises washing with deionized water to pH 5.4-5.6, and drying at 97-105 deg.C to water content of less than 10%.
5. The preparation method of the adsorbent for removing the phthalate plasticizer in the camellia oleosa seed oil according to claim 1, wherein the method comprises the following steps: the thinning method is to select 100-200 mesh products after crushing by a crusher.
6. An adsorbent for removing phthalate plasticizers from camellia oleosa seed oil prepared according to any one of claims 1-5, wherein: the surface area of the adsorbent is more than 1650m 2 The pore diameter is between 4.0nm and 4.5nm.
7. The use method of the adsorbent for removing the phthalate plasticizer in the camellia seed oil according to claim 6 is characterized by comprising the following steps: camellia seed oil contaminated with phthalate plasticizers → adsorption with adsorbent → filtration → purified camellia seed oil.
8. The use method of the adsorbent for removing the phthalate plasticizer in the camellia seed oil according to claim 7, wherein the adsorbent is prepared from the following raw materials in parts by weight: the adsorbent is added according to the weight of 0.2-0.5% of the oil-tea camellia seed oil.
9. The use method of the adsorbent for removing the phthalate plasticizer from the camellia seed oil according to claim 8, wherein the adsorbent is prepared from the following raw materials in parts by weight: adsorbing with adsorbent at room temperature for 1.5-2.5 hr.
10. The use method of the adsorbent for removing the phthalate plasticizer in the camellia oleosa seed oil according to claim 7, wherein the adsorbent comprises the following steps: adding diatomite with the weight of 0.08-0.12% of that of the camellia seed oil into the camellia seed oil, stirring uniformly and filtering.
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