CN114682238A - Regeneration method of waste clay - Google Patents
Regeneration method of waste clay Download PDFInfo
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- CN114682238A CN114682238A CN202011626396.2A CN202011626396A CN114682238A CN 114682238 A CN114682238 A CN 114682238A CN 202011626396 A CN202011626396 A CN 202011626396A CN 114682238 A CN114682238 A CN 114682238A
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- Prior art keywords
- clay
- waste
- ionic liquid
- oil
- mixture
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- 239000004927 clay Substances 0.000 title claims abstract description 229
- 239000002699 waste material Substances 0.000 title claims abstract description 93
- 238000011069 regeneration method Methods 0.000 title description 2
- 239000002608 ionic liquid Substances 0.000 claims abstract description 10
- 238000004061 bleaching Methods 0.000 claims description 101
- 239000004519 grease Substances 0.000 claims description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 46
- 239000000203 mixture Substances 0.000 claims description 44
- 239000011831 acidic ionic liquid Substances 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 20
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 230000001172 regenerating effect Effects 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 3
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 claims description 3
- 229960001231 choline Drugs 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 20
- 238000004064 recycling Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 abstract description 2
- 239000003344 environmental pollutant Substances 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 84
- 235000019198 oils Nutrition 0.000 description 84
- 238000004042 decolorization Methods 0.000 description 47
- 238000003756 stirring Methods 0.000 description 28
- 239000003549 soybean oil Substances 0.000 description 25
- 235000012424 soybean oil Nutrition 0.000 description 25
- 239000012153 distilled water Substances 0.000 description 18
- 238000001914 filtration Methods 0.000 description 17
- 239000003925 fat Substances 0.000 description 14
- 235000019197 fats Nutrition 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000007670 refining Methods 0.000 description 5
- 235000005687 corn oil Nutrition 0.000 description 4
- 239000002285 corn oil Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000008399 tap water Substances 0.000 description 4
- 235000020679 tap water Nutrition 0.000 description 4
- 235000015112 vegetable and seed oil Nutrition 0.000 description 4
- 239000008158 vegetable oil Substances 0.000 description 4
- ZRGWIXMPMASFPS-UHFFFAOYSA-N 1-butyl-3-methyl-1,2-dihydroimidazol-1-ium;dihydrogen phosphate Chemical compound OP(O)([O-])=O.CCCC[NH+]1CN(C)C=C1 ZRGWIXMPMASFPS-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 235000019482 Palm oil Nutrition 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000002540 palm oil Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 239000003225 biodiesel Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000010411 cooking Methods 0.000 description 2
- ZPAKGDVDAFOWRO-UHFFFAOYSA-N hydrogen sulfate 1-(3-methyl-1H-imidazol-3-ium-2-yl)butane-1-sulfonic acid Chemical compound OS([O-])(=O)=O.CCCC(c1[nH]cc[n+]1C)S(O)(=O)=O ZPAKGDVDAFOWRO-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 description 1
- JIWPXWWZICHKEO-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;dihydrogen phosphate Chemical compound OP(O)([O-])=O.CCCC[N+]=1C=CN(C)C=1 JIWPXWWZICHKEO-UHFFFAOYSA-M 0.000 description 1
- KXCVJPJCRAEILX-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;hydrogen sulfate Chemical compound OS([O-])(=O)=O.CCCCN1C=C[N+](C)=C1 KXCVJPJCRAEILX-UHFFFAOYSA-M 0.000 description 1
- 229930195730 Aflatoxin Natural products 0.000 description 1
- XWIYFDMXXLINPU-UHFFFAOYSA-N Aflatoxin G Chemical compound O=C1OCCC2=C1C(=O)OC1=C2C(OC)=CC2=C1C1C=COC1O2 XWIYFDMXXLINPU-UHFFFAOYSA-N 0.000 description 1
- FMMWHPNWAFZXNH-UHFFFAOYSA-N Benz[a]pyrene Chemical compound C1=C2C3=CC=CC=C3C=C(C=C3)C2=C2C3=CC=CC2=C1 FMMWHPNWAFZXNH-UHFFFAOYSA-N 0.000 description 1
- 239000004484 Briquette Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- GUZGRLAFOZVQNW-UHFFFAOYSA-L OP([O-])([O-])=O.CCCCn1cc[n+](C)c1.CCCCn1cc[n+](C)c1 Chemical compound OP([O-])([O-])=O.CCCCn1cc[n+](C)c1.CCCCn1cc[n+](C)c1 GUZGRLAFOZVQNW-UHFFFAOYSA-L 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 235000019774 Rice Bran oil Nutrition 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 239000005409 aflatoxin Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002802 bituminous coal Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000021466 carotenoid Nutrition 0.000 description 1
- 150000001747 carotenoids Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229930002875 chlorophyll Natural products 0.000 description 1
- 235000019804 chlorophyll Nutrition 0.000 description 1
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 239000008157 edible vegetable oil Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 235000021588 free fatty acids Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000011828 neutral ionic liquid Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000003904 phospholipids Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000010773 plant oil Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000008165 rice bran oil Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 235000020238 sunflower seed Nutrition 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
- B01J20/3475—Regenerating or reactivating using a particular desorbing compound or mixture in the liquid phase
-
- 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
- C11B13/00—Recovery of fats, fatty oils or fatty acids from waste materials
- C11B13/04—Recovery of fats, fatty oils or fatty acids from waste materials from spent adsorption materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/74—Recovery of fats, fatty oils, fatty acids or other fatty substances, e.g. lanolin or waxes
Abstract
The invention adopts the ionic liquid to treat the waste argil, and the recovery rate of the oil adsorbed by the waste argil is more than 90 percent after the waste argil is treated, thereby reflecting the excellent oil recovery effect. Meanwhile, the reactivated clay obtained after the treatment of the waste clay has good decoloring performance, and the decoloring capacity of the reactivated clay reaches more than 95 percent of that of new clay. Therefore, the waste water can be reprocessed after being used, the purpose of recycling can be achieved, the sources of environmental pollutants are reduced, and sustainable development is facilitated.
Description
Technical Field
The invention belongs to the field of oil processing, and particularly relates to a method for regenerating waste carclazyte for decoloring oil.
Background
The activated clay is one of indispensable important processing aids in the oil and fat refining process, and can effectively adsorb pigments (carotenoid and chlorophyll) in the oil and fat and impurities (protein, phospholipid, saccharides and the like) in the oil and fat; meanwhile, the activated clay can also remove harmful substances (benzopyrene, aflatoxin and the like) in the oil, and the use of the activated clay provides guarantee for producing high-quality oil. According to different oil products, the addition amount of activated clay in the oil and fat decolorization process is generally between 1% and 5%, and the waste clay contains 20% to 50% of oil and fat. Since the vegetable oil in the spent bleaching clay contains a large amount of unsaturated bonds, spontaneous combustion easily occurs when the vegetable oil is contacted with air, and fire is caused, so that the vegetable oil needs to be disposed in time. At present, the waste argil is either sold at low price or directly treated as waste, so that great waste is caused, and the environment is also polluted.
At present, the recycling of grease in the waste argil mainly comprises the following steps: squeezing, weak alkaline water cooking, solvent extraction, and surfactant. Although the pressing method has simple process, the oil recovery rate is limited, the residual oil content of the waste argil is still 20-25%, and the method has serious abrasion to equipment. Although the solvent extraction method has high oil recovery rate, the method has the defects of complex process, large solvent consumption, high requirement on safety of production workshops, easy generation of secondary pollution, potential safety hazards and the like. Although the weak alkaline water cooking method can recover the oil in the waste clay, the oil and the clay are difficult to separate, and the deoiled waste clay can not be regenerated. Although the recovery rate of oil and fat is high in the surfactant method, it takes a long time and it is difficult to break the emulsion formed.
In order to fully utilize the resource of the waste clay, many scientific research personnel at home and abroad develop a plurality of researches on the comprehensive utilization of the waste clay, and the invention patents also exist:
a process for treating spent bleaching earth is disclosed in CN 200410022931.8. The treatment process mainly comprises the steps of mixing the waste argil with the fine bituminous coal and water, extruding the mixture into a coal rod or a coal briquette to be used as fuel for combustion, and the problem of recycling of oil in the waste argil is not considered, and the problem of recycling of the waste argil is not solved.
CN00132233.8 discloses mixing n-hexane with waste clay, fully mixing the mixture in a closed mixing tank with stirring, and filtering and evaporating the mixture to recover oil, but it does not mention how the treated clay is used, and the reuse of clay is not achieved.
CN99150080.X discloses a method for regenerating waste clay for decoloring petroleum by soaking in industrial ethanol, which comprises washing the waste clay with industrial ethanol, recovering washed clay, and drying to regenerate the clay to achieve 96% of original decoloring activity. However, industrial ethanol is not suitable for being applied to industries such as food and the like with high safety requirements.
CN201110446667.0 discloses that two polar solvents are used to leach the waste clay, and desolventizing treatment is required after leaching, and the degree of restoration of decolorization power of the regenerated waste clay is also limited.
From the existing patents, various methods for treating the waste argil have certain defects, the problems of recycling of oil and fat in the waste argil and recycling of the waste argil cannot be simultaneously and effectively solved, and the subsequent activation process is complicated, so that the practical significance is low.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a novel method for regenerating waste clay, and the oil adsorbed by the waste clay is recovered.
In one aspect, the invention provides a method for regenerating spent bleaching clay, which comprises the steps of contacting an acidic ionic liquid with spent bleaching clay to obtain a spent bleaching clay mixture; and separating the spent bleaching clay mixture to obtain regenerated bleaching clay.
In another aspect, the invention also provides a method for recovering grease from waste clay, which comprises the steps of contacting an acidic ionic liquid with the waste clay to obtain a waste clay mixture; and separating the waste clay mixture to obtain the recovered grease.
In one or more embodiments, the spent bleaching earth mixture comprises water, and/or the contacting is by thermally reacting the spent bleaching earth mixture comprising spent bleaching earth, acidic ionic liquid, and water.
In one or more embodiments, the acidic ionic liquid includes any one or a combination of more of chloroaluminate acidic ionic liquids, carboxyl acidic ionic liquids, sulfonic acid acidic ionic liquids, benzenesulfonic acid acidic ionic liquids, imidazole acidic ionic liquids, amide acidic ionic liquids, choline acidic ionic liquids, benzimidazole acid ionic liquids, and triethylamine biacid ionic liquids.
In one or more embodiments, the method includes one or more of the following features:
1) the thermal reaction temperature is 140-300 ℃, or 150-280 ℃, or 160-220 ℃;
2) the thermal reaction time is 1-20h, or 2-15h, or 10-15 h;
3) the oil content of the waste argil is 10-50 wt%;
4) the waste clay mixture contains water, and the weight of the water is 1-10 times, or 2-5 times, or 2-3 times of the weight of the waste clay;
5) the weight of the acid ions in the waste argil mixture is 0.1-20% of the weight of the waste argil, or 0.5-10%.
In one or more embodiments, the step of separating the spent clay mixture to obtain regenerated clay specifically includes the following features:
carrying out solid-liquid separation on the waste argil mixture to obtain a waste argil phase; and/or
And washing and/or drying the waste clay phase to obtain the regenerated clay.
In another aspect, the present invention also provides a clay that is a regenerated clay obtained according to the above process.
In one or more embodiments, the step of separating the spent bleaching earth mixture to obtain the grease specifically includes the following features:
carrying out solid-liquid separation on the waste argil mixture to obtain a grease phase; and/or
And washing and/or drying the grease phase to obtain the recovered grease.
In one or more embodiments, the solid-liquid separation further comprises a step of reducing the temperature of the obtained mixed material, for example, reducing the temperature to below 100 ℃.
In another aspect, the present invention also provides a reclaimed oil or fat obtained by the above method.
The invention has the beneficial effects that:
1. the ionic liquid used in the invention is a green solvent, and in the process of treating the waste argil, the ionic liquid acts as a catalyst, water acts as a solvent, and after the reaction is finished, the separated argil only needs to be washed by water and does not need to be desolventized, so that the generation amount of waste water is reduced, and the method is clean and environment-friendly.
2. The reaction is carried out in a high-temperature reaction kettle, and the polarity of polar substances (such as water molecules) is obviously reduced under the high-temperature condition, so that the nonpolar oil in the waste argil is easily adsorbed, and the adsorption quantity is increased.
3. The invention can activate the argil while recovering the grease by one step, thereby realizing the purposes of less energy consumption and effective resource utilization.
Detailed Description
To make the features and effects of the present invention comprehensible to those skilled in the art, general description and definitions are made below with reference to terms and expressions mentioned in the specification and claims. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The theory or mechanism described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, i.e., the present disclosure may be practiced without limitation to any particular theory or mechanism.
All features defined herein as numerical ranges or percentage ranges, such as amounts, levels and concentrations, are for brevity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to cover and specifically disclose all possible subranges and individual numerical values (including integers and fractions) within the range. Herein, the percentage is a mass percentage unless otherwise specified.
In this context, for the sake of brevity, not all possible combinations of features in the various embodiments or examples are described. Therefore, the respective features in the respective embodiments or examples may be arbitrarily combined as long as there is no contradiction between the combinations of the features, and all the possible combinations should be considered as the scope of the present specification.
Various aspects of the invention are described below:
raw materials
In the present invention, the raw material used is "spent clay", and the source of spent clay is not limited in the present invention. In a specific embodiment, the waste clay is derived from oil-decolorizing waste clay of Shanghai Jiali food industry Limited, the components of the waste clay mainly comprise silicon dioxide and adsorbed grease, and the weight content of the grease in the waste clay is 10-50 wt%, namely the weight content of the adsorbed grease and impurities in the whole waste clay is 10-50 wt% (determined according to the method of GB/T14488.1-2008 plant oil content). The decolored oil in the decolored oil waste argil is soybean oil, corn oil, sunflower seed oil, rice oil, cottonseed oil, palm oil and coconut oil.
Acidic ionic liquid treatment
The acidic ionic liquid treatment step comprises the steps of carrying out thermal reaction on the waste argil, water and the acidic ionic liquid, and recovering grease and revived argil after the thermal reaction is finished.
The ionic liquid is salt which is liquid at or close to room temperature and completely consists of anions and cations, is also called low-temperature molten salt, and can be divided into Lewis acidic, Lewis alkaline, Br phi nsted acidic, Br phi nsted alkaline and neutral ionic liquid according to the acidity and alkalinity of the ionic liquid. Acidic ionic liquids are ionic liquids that can donate protons or gain electrons. All acidic ionic liquids are suitable for use in the present invention. For example, chloroaluminate acidic ionic liquid, carboxyl acidic ionic liquid, sulfonic acid acidic ionic liquid, benzenesulfonic acid acidic ionic liquid, imidazole acidic ionic liquid, amide acidic ionic liquid, choline acidic ionic liquid, benzimidazole acidic ionic liquid, triethylamine biacid ionic liquid, and the like. Optionally, the acidic ionic liquids used in the present invention include, but are not limited to, 1-butyl-3-methylimidazolium dihydrogen phosphate (BmimH)2PO4) 1-butyl-3-methylimidazolium hydrogen phosphate (BmimHPO)4) And 1-sulfonic acid butyl-3-methylimidazolium hydrogen sulfate (PSmimHSO)4) And the like.
In one embodiment, the amount of acidic ionic liquid may be from 0.1% to 20%, preferably from 0.5% to 10%, of the amount of spent bleaching earth.
The water used in the present invention refers to tap water, drinking water or distilled water, and in one embodiment, the amount of water may be 1 to 10 times, or 2 to 5 times, or 2 to 3 times the amount of spent bleaching earth.
The thermal reaction of the invention is that reaction materials are added into a high-temperature reaction kettle, each valve of the reaction kettle is sealed, heating is started under the condition of stirring, the temperature of the materials is raised, and after the temperature reaches a set value, the materials are kept warm and are continuously stirred. In one embodiment, the set temperature, i.e., the suitable temperature for the thermal reaction, is 140-. The holding time, i.e. the suitable time for the thermal reaction, is 1-20h, alternatively 2-15h, alternatively 10-15 h.
The acidic ionic liquid and water used in the invention are in a high-temperature reaction kettle, and the high temperature and high pressure can ensure that the temperature can reach 100-374 ℃. And, due to the high temperature, the polarity of polar substances (such as water molecules) is remarkably reduced, so that nonpolar oil and fat in the spent bleaching clay are easily adsorbed, and the adsorption amount is increased.
Recovered and regenerated argil
And (4) carrying out post-treatment on the waste argil after the acidic ionic liquid is treated. And cooling the mixed material obtained after the thermal reaction, wherein the obtained mixed material is a mixture containing a solid phase, a water phase and a grease phase. The spent bleaching earth is separated in a convenient manner commonly used in the art, for example, by centrifugation, filtration or natural sedimentation. When natural sedimentation is adopted, the upper grease layer is taken out, and the residual lower spent bleaching earth is washed by water, dried and crushed. Specifically, the regenerated argil can be dried in an oven at about 105 ℃ until the moisture content is less than 12%, and then the obtained product is crushed and sieved by a 200-mesh sieve, so that the undersize product is the regenerated argil.
Recovery of oil and fat
The lipidic phase separated from the work-up of the spent bleaching earth after the acidic ionic liquid treatment is purified in a manner that is easily conceivable in the art. When natural sedimentation is adopted, the upper grease layer is taken out, the grease layer contains impurities such as grease and partial suspended clay, and conventional filtration treatment can be carried out.
Application of regenerated clay
The regenerated clay has good decolorizing capability, so the regenerated clay can be used in oil and fat refining, in particular to edible oil decolorizing refining.
In one specific embodiment, the neutralized oil to be decolorized is weighed and placed in a reaction cup, regenerated clay is added to decolorize the oil by a conventional method, the mixed solution containing clay after decolorization is filtered while hot, and the color is measured by a 133.4mm colorimetric tank. And simultaneously, the color of the undecolored neutralized oil is measured by a colorimetric groove of 133.4 mm. And calculating the decolorization rate of the waste clay.
The decolorization ratio calculation mode is as follows:
r and Y are respectively the red value and the yellow value of the oil product measured by a Lovibond colorimeter, wherein before 10R + Y) is the color value of the oil product before decolorization, and after 10R + Y) is the color value of the oil product after decolorization.
The calculation mode of the decolorizing capacity is as follows:
percent decolorization ═ 100% (decolorization ratio of the adsorbent to be tested ÷ decolorization ratio of the standard adsorbent).
The inventors found that the regenerated spent clay is used for the decolorization of fats and oils, which has almost the same decolorization ability as that of fresh clay. Its decolouring power can be up to above 95% of new argil.
Application of recovered grease
The fat obtained by the method for treating regenerated spent bleaching clay of the present invention, namely, recovered fat, contains a large amount of compounds such as triglycerides and free fatty acids. Its application in industry and food is very wide. In one particular application, the recovered grease may be used to prepare biodiesel. Specifically, with reference to relevant parts in CN101240181, the treated recovered grease and methanol or ethanol are heated to a temperature required for reaction, then sodium hydroxide (accounting for 1% of the weight of the grease) or sodium methoxide is added as a catalyst, corresponding fatty acid methyl ester or ethyl ester is generated after reaction for a period of time, and then the biodiesel is obtained by washing and drying.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental methods of the following examples, which are not specified under specific conditions, are generally determined according to national standards. If there is no corresponding national standard, it is carried out according to the usual international standards, to the conventional conditions or to the conditions recommended by the manufacturer.
Unless defined or stated otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention.
The acidic ionic liquids of the present invention were purchased from: institute of chemical and physical research, Lanzhou, China academy of sciences
The oil content of the argil is measured according to the method of GB/T14488.1-2008 measuring the oil content of the vegetable oil.
The first embodiment is as follows:
100 g of soybean oil decoloration spent bleaching clay is taken, 1-butyl-3-methylimidazole dihydrogen phosphate (BmimH)2PO4)2.0 g of distilled water and 300 g of distilled water are put into a 1L reaction kettle, the temperature is increased to 180 ℃ under the condition of stirring at the rotating speed of 100rpm, the stirring is carried out for 10 hours, the temperature is reduced to 60 ℃, the mixture is kept still for 2 hours, an upper grease layer is absorbed, and the weight of the mixture is measured after the filtration. 18.73 g of grease is obtained. Drying the deoiled spent bleaching clay, and measuring the residual oil of the deoiled spent bleaching clay. The residual oil of the spent bleaching clay is reduced from 20.39 percent to 0.38 percent. The oil recovery rate was 91.85%. After being washed by water, the deoiled waste clay is dried in a drying oven at 105 ℃ for 1 hour, the moisture of the deoiled waste clay is measured to be 8.98 percent, and after being crushed, the deoiled waste clay is sieved by a 200-mesh sieve, so that 75.36 grams of regenerated clay is obtained. The decolorization rate of the regenerated clay is measured by using the neutralized soybean oil, and the decolorization force of the regenerated clay is 96 percent of that of the new clay.
Example two:
100 g of soybean oil decoloration spent bleaching clay is taken, 1-butyl-3-methylimidazole dihydrogen phosphate (BmimH)2PO4)8.0 g of distilled water and 250 g of distilled water are put into a 1L reaction kettle, the temperature is raised to 220 ℃ under the condition of stirring at the rotating speed of 100rpm, the stirring is carried out for 12 hours, the temperature is lowered to 60 ℃, the mixture is kept still for 2 hours, an upper grease layer is absorbed, and the weight of the mixture is measured after the filtration to obtain 18.65 g of grease. Drying the deoiled spent bleaching clay, and measuring the residual oil of the deoiled spent bleaching clay. The residual oil of the spent bleaching clay is reduced to 0.26 percent from 20.39 percent. The oil recovery rate was 91.47%. After being washed by water, the deoiled waste clay is dried in a drying oven at 105 ℃ for 1 hour, the moisture content is measured to be 9.29 percent, and after being crushed, the deoiled waste clay is sieved by a 200-mesh sieve, so 74.58 grams of regenerated clay is obtained. Determining the decolorization rate of the regenerated clay with neutralized soybean oil, and thenThe decolouring power of raw white clay is 99% of that of new white clay.
Example three:
80 g of waste clay for decolorizing palm oil (BmimHPO) which is 1-butyl-3-methylimidazole hydrophosphate4)7.2 g of distilled water and 240 g of distilled water are put into a 1L reaction kettle, the temperature is raised to 200 ℃ under the condition of stirring at the rotating speed of 100rpm, the stirring is carried out for 15 hours, the temperature is lowered to 80 ℃, the temperature is kept for 2 hours, an upper grease layer is absorbed, and the weight of the upper grease layer is measured after the filtration, so that 18.69 g of grease is obtained. Drying the deoiled spent bleaching clay, and measuring the residual oil of the deoiled spent bleaching clay. The residual oil of the spent bleaching clay is reduced from 25.26 percent to 0.41 percent. The oil recovery rate was 92.49%. After being washed by water, the deoiled waste clay is dried in a drying oven at 105 ℃ for 1 hour, the moisture content is measured to be 8.42 percent, and after being crushed, the deoiled waste clay is sieved by a 200-mesh sieve, so 54.83 grams of regenerated clay is obtained. The decolorization rate of the regenerated clay is measured by using the neutralized soybean oil, and the decolorization force of the regenerated clay is 100 percent of that of the new clay.
Example four:
100 g of corn oil decolorization spent bleaching clay and 3.0 g of 1-sulfobutyl-3-methylimidazole hydrogen sulfate (PSmimHSO)4) And 300 g of tap water are put into a 1L reaction kettle, the temperature is increased to 160 ℃ under the condition of stirring at the rotating speed of 150rpm, the stirring is carried out for 13 hours, the temperature is reduced to 60 ℃, the mixture is kept still for 2 hours, an upper grease layer is absorbed, and the weight of the upper grease layer is measured after the filtration, so that 20.46 g of grease is obtained. After the deoiled waste clay is dried, the residual oil of the deoiled waste clay is measured, the residual oil of the waste clay is reduced to 0.47 percent from 22.68 percent, and the oil recovery rate is 90.21 percent. The deoiled spent bleaching clay is washed by water and dried in a drying oven at 105 ℃ for 1 hour, the moisture content is measured to be 7.95 percent, and the deoiled spent bleaching clay is crushed and sieved by a 200-mesh sieve to obtain 72.89 g of regenerated bleaching clay. The decolorization rate of the regenerated clay is measured by using the neutralized soybean oil, and the decolorization force of the regenerated clay is 95 percent of that of the new clay.
Example five:
100 g of rice bran oil decoloration spent bleaching clay, 1-sulfobutyl-3-methylimidazole bisulfate (PSmimHSO)4)2.5 g of distilled water and 280 g of distilled water are put into a 1L reaction kettle, the temperature is raised to 190 ℃ under the condition of stirring at the rotating speed of 120rpm, the stirring is carried out for 8 hours, the temperature is lowered to 60 ℃, the mixture is kept still for 2 hours, an upper grease layer is absorbed, and the weight of the mixture is measured after the filtration to obtain 21.99 g of grease. Deoiling waste whiteAfter the soil is dried, the residual oil is measured, the residual oil of the waste clay is reduced from 23.84 percent to 0.42 percent, and the oil recovery rate is 92.24 percent. The deoiled spent bleaching clay is washed by water and dried in a drying oven at 105 ℃ for 1 hour, the moisture content is measured to be 7.76 percent, and the deoiled spent bleaching clay is crushed and sieved by a 200-mesh sieve to obtain 72.56 grams of regenerated bleaching clay. The decolorization rate of the regenerated clay is measured by using the neutralized soybean oil, and the decolorization force of the regenerated clay is 97 percent of that of the new clay.
Example six:
50 g of spent bleaching earth obtained by decoloring soybean oil, 1-butyl-3-methylimidazole dihydrogen phosphate (BmimH2 PO)4)10.0 g of distilled water and 500 g of distilled water are put into a 1L reaction kettle, the temperature is raised to 140 ℃ under the condition of stirring at the rotating speed of 100rpm, the stirring is carried out for 20 hours, the temperature is lowered to 60 ℃, the mixture is kept still for 2 hours, an upper grease layer is absorbed, and the weight of the mixture is measured after the filtration. 9.40 g of grease is obtained. Drying the deoiled spent bleaching clay, and measuring the residual oil of the deoiled spent bleaching clay. The residual oil of the spent bleaching clay is reduced to 0.36 percent from 20.39 percent. The oil recovery rate was 92.20%. The deoiled spent bleaching clay is dried in an oven at 105 ℃ for 1 hour after being washed by water, the moisture content is measured to be 8.69 percent, and the deoiled spent bleaching clay is crushed and sieved by a 200-mesh sieve to obtain 37.76 g of regenerated bleaching clay. The decolorization rate of the regenerated clay is measured by using the neutralized soybean oil, and the decolorization force of the regenerated clay is 98 percent of that of the new clay.
Example seven:
80 g of palm oil decoloration spent bleaching clay (BmimHPO)4)0.08 g of distilled water and 80 g of distilled water are put into a 1L reaction kettle, the temperature is raised to 300 ℃ under the condition of stirring at the rotating speed of 100rpm, the stirring is carried out for 1 hour, the temperature is lowered to 80 ℃, the temperature is kept for 2 hours, an upper grease layer is absorbed, and the weight of the upper grease layer is measured after the filtration, so that 18.43 g of grease is obtained. Drying the deoiled spent bleaching clay, and measuring the residual oil of the deoiled spent bleaching clay. The residual oil of the spent bleaching clay is reduced from 25.26 percent to 0.19 percent. The oil recovery rate was 91.20%. The deoiled spent bleaching clay is dried in an oven at 105 ℃ for 1 hour after being washed by water, the moisture content is measured to be 8.21 percent, and the deoiled spent bleaching clay is crushed and sieved by a 200-mesh sieve to obtain 54.96 grams of regenerated bleaching clay. The decolorization ratio of the regenerated clay is measured by using the neutralized soybean oil, and the decolorization force of the regenerated clay is 102 percent of that of the new clay.
Comparative example one:
100 g of soybean oil decolorization spent bleaching clay and 300 g of distilled water are taken and placed in a 1L reaction kettle, the temperature is raised to 130 ℃ under the condition of stirring at the rotating speed of 100rpm, the stirring is carried out for 20 hours, the temperature is lowered to 60 ℃, the standing is carried out for 2 hours, and no oil can be separated out from the upper layer. And drying the treated waste argil, and measuring residual oil of the treated waste argil. The residual oil of the spent bleaching clay is reduced from 20.39 percent to 20.28 percent, and almost no change is caused. The deoiled spent bleaching clay is dried in a drying oven at 105 ℃ for 1 hour after being filtered, the moisture content is measured to be 8.98 percent, and the deoiled spent bleaching clay is sieved by a 200-mesh sieve after being crushed, so 99.16 grams of regenerated bleaching clay is obtained. The decolorization rate of the regenerated clay is measured by using the neutralized soybean oil, and the decolorization force of the regenerated clay is 12 percent of that of the new clay.
Comparative example two:
100 g of soybean oil decolorization spent bleaching clay and 300 g of n-hexane are taken and placed in a 1L three-neck flask, the temperature is raised to 50 ℃, the rotation speed is 150rpm, the stirring is carried out for 10 hours, the filtration is carried out, the n-hexane is evaporated and recovered by a rotary evaporator, the weight of the recovered grease is measured, and 18.58 g of grease is obtained. Drying the deoiled spent bleaching clay, and measuring the residual oil of the deoiled spent bleaching clay. The residual oil of the waste argil is reduced from 20.39 percent to 0.88 percent. The oil recovery rate was 91.12%. The deoiled spent bleaching clay is dried in an oven at 105 ℃ for 1 hour, the moisture of the deoiled spent bleaching clay is measured to be 5.63 percent, and the deoiled spent bleaching clay is crushed and then sieved by a 200-mesh sieve to obtain 76.28 grams of regenerated bleaching clay. The decolorization rate of the regenerated clay is measured by using the neutralized soybean oil, and the decolorization force of the regenerated clay is 8 percent of that of the new clay.
Comparative example three:
100 g of corn oil decolorization spent bleaching clay, 300 g of tap water and 5 g of sodium hydroxide are taken and placed in a 1L reaction kettle, the temperature is raised to 210 ℃ under the condition of stirring at the rotating speed of 150rpm, the mixture is stirred for 13 hours, the temperature is reduced to 60 ℃, the mixture is kept still for 2 hours, an upper grease layer is absorbed, and after filtration, the weight of the upper grease layer is measured to obtain 14.25 g of grease. After the deoiled waste clay is dried, the residual oil of the deoiled waste clay is measured, the residual oil of the waste clay is reduced to 0.21 percent from 22.68 percent, and the oil recovery rate is 62.83 percent. The deoiled spent bleaching clay is dried in an oven at 105 ℃ for 1 hour, the moisture of the deoiled spent bleaching clay is measured to be 6.79 percent, and the deoiled spent bleaching clay is crushed and then sieved by a 200-mesh sieve to obtain 74.13 grams of regenerated bleaching clay. The decolorization ratio of the regenerated clay is measured by using the neutralized soybean oil, and the decolorization force of the regenerated clay is 26 percent of the decolorization force of the new clay.
Comparative example four:
100 g of corn oil decolorization spent bleaching clay, 300 g of tap water and 5 g of sodium carbonate are taken and placed in a 1L reaction kettle, the temperature is raised to 210 ℃ under the condition of stirring at the rotating speed of 150rpm, the stirring is carried out for 13 hours, the temperature is reduced to 60 ℃, the standing is carried out for 2 hours, an upper grease layer is absorbed, the weight of the upper grease layer is measured after the filtration, and 16.31 g of grease is obtained. After the deoiled waste clay is dried, the residual oil of the deoiled waste clay is measured, the residual oil of the waste clay is reduced to 1.12 percent from 22.68 percent, and the oil recovery rate is 71.91 percent. The deoiled spent bleaching clay is dried in a drying oven at 105 ℃ for 1 hour, the moisture of the deoiled spent bleaching clay is measured to be 8.22 percent, and the deoiled spent bleaching clay is crushed and then sieved by a 200-mesh sieve to obtain 72.08 grams of regenerated bleaching clay. The decolorization rate of the regenerated clay is measured by using the neutralized soybean oil, and the decolorization force of the regenerated clay is 45 percent of that of the new clay.
Comparative example five:
100 g of soybean oil decolorized spent bleaching clay, 300 g of distilled water and 5 g of potassium hydroxide are put into a 1L reaction kettle, the temperature is raised to 200 ℃ under the condition of stirring at the rotating speed of 150rpm, the mixture is stirred for 15 hours, the temperature is reduced to 60 ℃, the mixture is kept still for 2 hours, an upper grease layer is absorbed, and after filtration, the weight of the upper grease layer is measured to obtain 14.21 g of grease. The residual oil of the spent bleaching clay is reduced to 0.51 percent from 20.39 percent. The oil recovery rate was 69.69%. The deoiled spent bleaching clay is dried in an oven at 105 ℃ for 1 hour, the moisture content is measured to be 7.72 percent, and the deoiled spent bleaching clay is crushed and sieved by a 200-mesh sieve to obtain 75.10 g of regenerated bleaching clay. The decolorization rate of the regenerated clay is measured by using the neutralized soybean oil, and the decolorization force of the regenerated clay is 12 percent of that of the new clay.
Comparative example six:
100 g of soybean oil decolorized spent bleaching clay, 300 g of distilled water and 10 g of 98% sulfuric acid are taken and placed in a 1L reaction kettle, the temperature is raised to 200 ℃ under the condition of stirring at the rotating speed of 150rpm, the stirring is carried out for 15 hours, the temperature is reduced to 60 ℃, the standing is carried out for 2 hours, an upper layer grease layer is absorbed, and the weight of the grease layer is measured after the filtration, so as to obtain 17.21 g of grease. The residual oil of the spent bleaching clay is reduced to 1.89 percent from 20.39 percent. The oil recovery rate was 84.40%. The deoiled spent bleaching clay is dried in an oven at 105 ℃ for 1 hour, the moisture of the deoiled spent bleaching clay is measured to be 6.77 percent, and the deoiled spent bleaching clay is sieved by a 200-mesh sieve after being crushed to obtain 73.26 grams of regenerated bleaching clay. The decolorization rate of the regenerated clay is measured by using the neutralized soybean oil, and the decolorization force of the regenerated clay is 79 percent of that of the new clay.
Comparative example seven:
100 g of soybean oil decolorized spent bleaching clay, 300 g of distilled water and 8 g of phosphoric acid are taken and placed in a 1L reaction kettle, the temperature is raised to 200 ℃ under the condition of stirring at the rotating speed of 150rpm, the stirring is carried out for 15 hours, the temperature is reduced to 60 ℃, the standing is carried out for 2 hours, an upper layer grease layer is absorbed, and the weight of the grease layer is measured after the filtration, so as to obtain 17.01 g of grease. The residual oil of the spent bleaching clay is reduced to 1.62 percent from 20.39 percent. The oil recovery rate was 83.42%. The deoiled spent bleaching clay is dried in an oven at 105 ℃ for 1 hour, the moisture of the deoiled spent bleaching clay is measured to be 6.77 percent, and the deoiled spent bleaching clay is sieved by a 200-mesh sieve after being crushed to obtain 73.26 grams of regenerated bleaching clay. The decolorization rate of the regenerated clay is measured by using the neutralized soybean oil, and the decolorization force of the regenerated clay is 72 percent of that of the new clay.
Comparative example eight:
100 g of soybean oil decolorized spent bleaching clay, 300 g of distilled water and 8 g of nitric acid are taken and placed in a 1L reaction kettle, the temperature is raised to 210 ℃ under the condition of stirring at the rotating speed of 150rpm, the mixture is stirred for 13 hours, the temperature is reduced to 60 ℃, the mixture is kept still for 2 hours, an upper grease layer is absorbed, and after filtration, the weight of the upper grease layer is measured to obtain 16.12 g of grease. The residual oil of the spent bleaching clay is reduced to 2.32 percent from 20.39 percent. The oil recovery rate was 79.06%. The deoiled spent bleaching clay is dried in an oven at 105 ℃ for 1 hour, the moisture content is measured to be 7.12 percent, and the deoiled spent bleaching clay is crushed and then sieved by a 200-mesh sieve to obtain 73.87 grams of regenerated bleaching clay. The decolorization rate of the regenerated clay is measured by using the neutralized soybean oil, and the decolorization force of the regenerated clay is 69 percent of that of the new clay.
The differences between the examples and comparative examples are summarized in the following table:
the tables show that the method can effectively extract the oil in the waste clay, and the deoiled clay after the oil extraction can be reused as fresh clay after being simply washed, dried and crushed. The process can realize the recycling of the argil while extracting the oil, reduce the generation of solid wastes in the oil refining process and greatly reduce the refining cost.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the scope of the invention, which is defined by the claims appended hereto, and any other technical entity or method that is encompassed by the claims as broadly defined herein, or equivalent variations thereof, is contemplated as being encompassed by the claims.
Claims (10)
1. The method for regenerating the waste clay is characterized by comprising the steps of contacting an acidic ionic liquid with the waste clay to obtain a waste clay mixture; and separating the spent bleaching clay mixture to obtain regenerated bleaching clay.
2. The method for recovering grease from waste clay is characterized by comprising the steps of contacting an acidic ionic liquid with the waste clay to obtain a waste clay mixture; and separating the waste clay mixture to obtain the recovered grease.
3. The process of claim 1 or 2, wherein the spent bleaching earth mixture comprises water, and/or the contacting is by thermally reacting the spent bleaching earth mixture comprising spent bleaching earth, acidic ionic liquid, and water.
4. The method of claim 1 or 2, wherein the acidic ionic liquid comprises any one or more of chloroaluminate acidic ionic liquid, carboxyl acidic ionic liquid, sulfonic acid acidic ionic liquid, benzenesulfonic acid acidic ionic liquid, imidazole acidic ionic liquid, amide acidic ionic liquid, choline acidic ionic liquid, benzimidazole acid ionic liquid and triethylamine bi-acidic ionic liquid.
5. The method of claim 3 or 4, comprising one or more of the following features:
1) the thermal reaction temperature is 140-300 ℃, or 150-280 ℃, or 160-220 ℃;
2) the thermal reaction time is 1-20h, or 2-15h, or 10-15 h;
3) the oil content of the waste argil is 10-50 wt%;
4) the waste clay mixture contains water, and the weight of the water is 1-10 times, or 2-5 times, or 2-3 times of the weight of the waste clay;
5) the weight of the acid ions in the waste clay mixture is 0.1-20% of the weight of the waste clay, or 0.5-10%.
6. The method of claim 1, wherein the step of separating the spent clay mixture to obtain regenerated clay specifically comprises the following characteristics:
carrying out solid-liquid separation on the waste clay mixture to obtain a waste clay phase; and/or
And washing and/or drying the waste clay phase to obtain the regenerated clay.
7. The method of claim 2, wherein the step of separating the spent bleaching clay mixture to obtain the oil comprises the following specific features:
carrying out solid-liquid separation on the waste argil mixture to obtain an oil phase; and/or
And washing and/or drying the grease phase to obtain the recovered grease.
8. The method of claim 6 or 7, further comprising the step of reducing the temperature of the resulting mixture, e.g. to below 100 ℃, prior to the solid-liquid separation.
9. Regenerated clay obtained by the process of claim 1 or 6.
10. A recovered oil or fat obtained by the method according to claim 2 or 7.
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| WO2024023370A1 (en) * | 2022-07-28 | 2024-02-01 | Solució Circular S.L. | Reactor, installation and associated operation process for the extraction of oil from spent earth and the reactivation of said earth |
| CN115353933A (en) * | 2022-10-19 | 2022-11-18 | 苏州丰倍生物科技股份有限公司 | Method for recovering grease from waste clay |
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| CN114682238B (en) | 2024-03-01 |
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