CN114682238B - Regeneration method of waste clay - Google Patents
Regeneration method of waste clay Download PDFInfo
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- CN114682238B CN114682238B CN202011626396.2A CN202011626396A CN114682238B CN 114682238 B CN114682238 B CN 114682238B CN 202011626396 A CN202011626396 A CN 202011626396A CN 114682238 B CN114682238 B CN 114682238B
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- clay
- ionic liquid
- bleaching clay
- spent bleaching
- acidic ionic
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- 239000004927 clay Substances 0.000 title claims abstract description 281
- 239000002699 waste material Substances 0.000 title claims abstract description 49
- 238000011069 regeneration method Methods 0.000 title description 3
- 239000004519 grease Substances 0.000 claims abstract description 83
- 238000000034 method Methods 0.000 claims abstract description 50
- 238000004061 bleaching Methods 0.000 claims description 167
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 60
- 239000011831 acidic ionic liquid Substances 0.000 claims description 59
- 238000006243 chemical reaction Methods 0.000 claims description 39
- 239000000203 mixture Substances 0.000 claims description 36
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 5
- 230000001172 regenerating effect Effects 0.000 claims description 5
- 150000001408 amides Chemical class 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 claims description 4
- 229960001231 choline Drugs 0.000 claims description 4
- 150000004841 phenylimidazoles Chemical class 0.000 claims description 4
- 238000011084 recovery Methods 0.000 abstract description 23
- 239000002608 ionic liquid Substances 0.000 abstract description 7
- 238000004064 recycling Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 239000003344 environmental pollutant Substances 0.000 abstract 1
- 238000012958 reprocessing Methods 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 65
- 235000019198 oils Nutrition 0.000 description 65
- 238000004042 decolorization Methods 0.000 description 32
- 238000003756 stirring Methods 0.000 description 27
- 239000003549 soybean oil Substances 0.000 description 24
- 235000012424 soybean oil Nutrition 0.000 description 24
- 238000001914 filtration Methods 0.000 description 15
- 239000012153 distilled water Substances 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
- 239000012071 phase Substances 0.000 description 7
- 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 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000003925 fat Substances 0.000 description 5
- 235000019197 fats Nutrition 0.000 description 5
- 238000007670 refining Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 235000015112 vegetable and seed oil Nutrition 0.000 description 5
- 239000008158 vegetable oil Substances 0.000 description 5
- 235000005687 corn oil Nutrition 0.000 description 4
- 239000002285 corn oil Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000008399 tap water Substances 0.000 description 4
- 235000020679 tap water Nutrition 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 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
- 235000013305 food Nutrition 0.000 description 3
- 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 3
- 239000012535 impurity Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002540 palm oil Substances 0.000 description 3
- 238000004062 sedimentation Methods 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
- 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
- 230000007547 defect Effects 0.000 description 2
- 230000029087 digestion Effects 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 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
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 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
- 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
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 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
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 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
- 230000008859 change Effects 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
- 239000002385 cottonseed oil Substances 0.000 description 1
- 235000012343 cottonseed oil Nutrition 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
- 238000002474 experimental method Methods 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 239000000706 filtrate Substances 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
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 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
- 239000002798 polar solvent Substances 0.000 description 1
- 238000001556 precipitation Methods 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
- 230000008929 regeneration Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000008165 rice bran oil Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 235000020238 sunflower seed Nutrition 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 239000002351 wastewater Substances 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 clay, and the recovery rate of the grease adsorbed by the waste clay is more than 90 percent after the treatment, thus showing excellent grease recovery effect. Meanwhile, the obtained reactivating clay after treating the waste clay has good decoloring performance, and the decoloring capacity of the reactivating clay reaches more than 95% of that of new white clay. Therefore, the method can be used for reprocessing after being used, can achieve the aim of recycling, reduces the source of environmental pollutants, and is beneficial to sustainable development.
Description
Technical Field
The invention belongs to the field of grease processing, and particularly relates to a method for regenerating spent bleaching clay for grease decoloring.
Background
Activated clay is one of essential processing aids in the oil refining process, and can effectively adsorb pigments (carotenoid, chlorophyll) in the oil and impurities (protein, phospholipid, saccharides and the like) in the oil; meanwhile, harmful substances (benzopyrene, aflatoxin and the like) in the grease can be removed from the activated clay, and the use of the activated clay provides a guarantee for producing high-quality grease. According to different oil products, the addition amount of the activated clay in the grease decoloring process is generally between 1% and 5%, and the waste clay contains 20-50% of grease. Since vegetable oil in spent bleaching clay contains a large amount of unsaturated bonds, spontaneous combustion easily occurs when the vegetable oil contacts with air, and fire is caused, so the vegetable oil must be disposed of in time. At present, the spent bleaching clay is sold at low price or is directly treated as waste, so that great waste is caused, and the environment is polluted.
At present, the recycling of the grease in the spent bleaching clay mainly comprises the following steps: a pressing method, a weak-base water digestion method, a solvent extraction method, and a surfactant method. The squeezing method has the advantages of simple process, limited oil recovery rate, 20-25% of spent bleaching clay residual oil and serious equipment abrasion. The solvent leaching method has the advantages of high oil recovery rate, complex process, high solvent consumption, high solvent loss, high safety requirement on production workshops, easiness in generating secondary pollution, potential safety hazard and the like. Although the weak alkaline water digestion method can recover the grease in the spent bleaching clay, the grease bleaching clay is difficult to separate, and the spent bleaching clay after deoiling can not be regenerated. The surfactant method has high oil recovery rate, but takes a long time, and the emulsion produced is difficult to break.
In order to fully utilize the resource of the spent bleaching clay, a plurality of scientific researchers at home and abroad develop a plurality of researches on the comprehensive utilization of the spent bleaching clay, and the invention also has the patent:
a method of treating spent bleaching clay is disclosed in CN 200410022931.8. The treatment process mainly comprises the steps of mixing the waste clay, the fine bituminous coal and the water, extruding the mixture into coal rods or coal balls for combustion as fuel, and not only is recycling of grease in the waste clay not considered, but also the problem of recycling of the waste clay is not solved.
CN00132233.8 discloses that n-hexane and spent clay are mixed and the mixture is fully mixed in a stirring and sealing mixing tank, and then the mixture is filtered and evaporated to recover grease, but it is not mentioned how the treated clay is used, and the recycling of clay is not realized.
In CN99150080.X, a method for regenerating petroleum decoloring waste clay by using industrial ethanol is disclosed, the waste clay is washed by industrial ethanol, and the recovered washed clay is dried and regenerated, so that the decoloring activity of the clay reaches 96% of the original activity. Industrial ethanol is not beneficial to the application in industries with high safety requirements such as food.
CN201110446667.0 discloses that the use of two polar solvents to leach spent bleaching clay requires a desolventizing treatment after leaching, and the recovery of bleaching power of the regenerated spent bleaching clay is limited.
From the prior patents, various methods for treating the spent bleaching clay have certain defects, can not effectively solve the problems of oil recovery in the spent bleaching clay and the recycling of the spent bleaching clay at the same time, and the subsequent activation process is complex, 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 the waste clay, and the grease adsorbed by the waste clay is recovered.
In one aspect, the present invention provides a method for regenerating spent bleaching clay, the method comprising 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 spent bleaching clay, the method comprising 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 the recovered grease.
In one or more embodiments, the spent bleaching clay mixture comprises water, and/or the contacting is by thermally reacting a spent bleaching clay mixture comprising spent bleaching clay, an acidic ionic liquid, and water.
In one or more embodiments, the acidic ionic liquid includes any one or more of chloroaluminate acidic ionic liquid, carboxyl acidic ionic liquid, sulfonic acidic ionic liquid, benzenesulfonic acidic ionic liquid, imidazole acidic ionic liquid, amide acidic ionic liquid, choline acidic ionic liquid, phenylimidazole salt acidic ionic liquid, and triethylamine double acidic ionic liquid.
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 10-15h;
3) The oil content of the spent bleaching clay is 10-50wt%;
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 that of the waste clay;
5) The weight of the acid ions in the spent bleaching clay mixture is 0.1-20% of the weight of the spent bleaching clay, or 0.5-10%.
In one or more embodiments, the step of separating the spent bleaching clay mixture to obtain a regenerated bleaching clay specifically includes the following features:
solid-liquid separation of the waste clay mixture to obtain waste clay phase; and/or
Washing and/or drying the spent bleaching clay phase to obtain regenerated bleaching clay.
In another aspect, the present invention also provides a clay which is a regenerated clay obtained according to the above method.
In one or more embodiments, the step of separating the spent bleaching clay mixture to obtain grease specifically includes the following features:
solid-liquid separation is carried out on the spent bleaching clay mixture to obtain an oil 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 may further comprise a step of cooling the resulting mixture, for example, to a temperature below 100 ℃.
In another aspect, the invention also provides a recovered oil obtained by the 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 spent bleaching clay, the ionic liquid plays a role of a catalyst, water is used as a solvent, and after the reaction is finished, the separated bleaching clay only needs to be washed with water and does not need to be desolventized, so that the wastewater yield 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 nonpolar grease in the spent bleaching clay is easily adsorbed, and the adsorption quantity is increased.
3. The invention can recover grease and activate clay in one step, thereby realizing the purposes of low energy consumption and effective utilization of resources.
Detailed Description
So that those skilled in the art can appreciate the features and effects of the present invention, a general description and definition of the terms and expressions set forth in the specification and claims follows. Unless otherwise defined, 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, and in the event of a conflict, the present specification shall control.
The theory or mechanism described and disclosed herein, whether right or wrong, is not meant to limit the scope of the invention in any way, i.e., the present disclosure may be practiced without limitation to any particular theory or mechanism.
In this document, all features such as amounts, and concentrations that may be recited with numerical ranges or percent ranges are presented herein for simplicity and convenience only. Accordingly, the description of a numerical range or percentage range should be considered to cover and specifically disclose all possible sub-ranges and individual values (including integers and fractions) within the range. Herein, unless otherwise specified, the percentages are mass percentages.
In this context, not all possible combinations of the individual technical features in the individual embodiments or examples are described in order to simplify the description. Accordingly, as long as there is no contradiction between the combinations of these technical features, any combination of the technical features in the respective embodiments or examples is possible, and all possible combinations should be considered as being within 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 bleaching clay", and the present invention is not limited to the origin of spent bleaching clay, unless otherwise specified. In one embodiment, the spent bleaching clay is derived from a spent bleaching clay of Shanghai Jia food industry Co., ltd. De-oiled oil, the spent bleaching clay comprises mainly silica and adsorbed fat, the weight content of fat in the spent bleaching clay is 10-50wt%, i.e. the weight content of adsorbed fat and impurities in the whole spent bleaching clay is 10-50wt% (measured according to the method "GB/T14488.1-2008 vegetable oil content measurement"). The decolorized oil in the decolorized oil spent bleaching clay refers to soybean oil, corn oil, sunflower seed oil, rice oil, cotton seed 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 spent bleaching clay, water and acidic ionic liquid, and recovering grease and revived bleaching clay after the thermal reaction is finished.
The ionic liquid is a salt which is liquid at room temperature or near room temperature and is composed of anions and cations, also called as low-temperature molten salt, and the ionic liquid can be classified into Lewis acidity and Lewis according to the acidity and alkalinity of the ionic liquids alkaline, brPhinsted acidic, brPhinsted alkaline and neutral ionic liquids. Acidic ionic liquids refer to ionic liquids that can provide protons or give electrons. All acidic ionic liquids are suitable for use in the present invention. For example, 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, phenylimidazole salt acidic ionic liquids, triethylamine double acidic ionic liquids, and the like. Optionally, the acidic ionic liquids used in the present invention include, but are not limited to, 1-butyl-3-methylimidazole dihydrogen phosphate (BmimH) 2 PO 4 ) 1-butyl-3-methylimidazole hydrogen phosphate (BmimHPO) 4 ) And 1-sulfobutyl-3-methylimidazole bisulfate (PSmimHSO) 4 ) Etc.
In one embodiment, the acidic ionic liquid may be used in an amount of 0.1% to 20%, preferably 0.5% to 10% of the amount of spent bleaching clay.
The water used in the present invention refers to tap water or 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 clay.
The thermal reaction of the invention is to add the reaction materials into a high-temperature reaction kettle, seal each valve of the reaction kettle, start heating under the condition of stirring, heat the materials, keep the temperature and continue stirring after the temperature reaches a set value. In one embodiment, the set temperature, i.e., the suitable temperature for the thermal reaction, is 140-300 ℃, alternatively 150-280 ℃, alternatively 160-220 ℃. The holding time, i.e. the suitable time for the thermal reaction, is 1-20 hours, alternatively 2-15 hours, alternatively 10-15 hours.
The acidic ionic liquid and water used in the invention are in a high-temperature reaction kettle, and the high temperature and the high pressure enable the temperature to reach the high temperature of 100-374 ℃. In addition, due to the effect of the high temperature, the polarity of polar substances (such as water molecules) is obviously reduced, so that nonpolar grease in the waste clay is easily adsorbed, and the adsorption quantity is increased.
Recovery of regenerated clay
And (3) carrying out post-treatment on the spent bleaching clay treated by the acidic ionic liquid. And cooling the mixture obtained after the thermal reaction, wherein the obtained mixture is a mixture containing a solid phase, a water phase and a grease phase. The spent bleaching clay may be separated in a convenient separation manner commonly used in the art, and may be, for example, centrifugation, filtration or natural sedimentation stratification. When natural sedimentation is adopted, the upper grease layer is taken out, and the rest lower spent bleaching clay is washed with water, dried and crushed. Specifically, the clay can be dried in an oven at about 105 ℃ until the water content is less than 12%, crushed and then screened by a 200-mesh sieve, and the undersize is the regenerated clay.
Recovery of oil
The fat phase separated by post-treatment of spent bleaching clay treated with acidic ionic liquid is purified in a manner readily apparent to those skilled in the art. When natural sedimentation is adopted, the upper grease layer is taken out, and the grease layer contains grease, part of suspended clay and other impurities, so that conventional filtering treatment can be carried out.
Application of regenerated clay
The regenerated clay has better decoloring capability, so that the regenerated clay can be used in oil refining, in particular to decoloring refining of edible oil.
In one embodiment, the neutral oil to be decolorized is weighed and placed in a reaction cup, regenerated clay is added, grease decolorization is carried out in a conventional method, the decolorized mixed solution containing clay is filtered while hot, and the color is measured by a 133.4mm colorimetric tank. The color of the undeloured neutralized oil was also determined using a 133.4mm cuvette. And calculating the decoloring rate of the spent bleaching clay.
The decoloring rate is calculated by the following steps:
r and Y are respectively the red value and the yellow value of the oil product measured by a Rovinone colorimeter, the color value of the oil product before decolorization is shown before (10R+Y), and the color value of the oil product after decolorization is shown after (10R+Y).
The decoloring force calculation mode is as follows:
the% decolorizing force = (decolorizing rate of adsorbent to be measured +.decolorizing rate of standard adsorbent) × 100%.
The inventors found that the regenerated spent bleaching clay is used for the decolorization of fats and oils, and has almost the same decolorizing capacity as fresh white clay. The decoloring force of the clay can reach more than 95% of that of new clay.
Application of recovered grease
The oil obtained by the treatment method of the regenerated spent bleaching clay of the present invention contains a large amount of compounds such as triglycerides and free fatty acids, as recovered oil. Its application in industry and food is very extensive. In one particular application, the recovered oil may be used to prepare biodiesel. Specifically, referring to the relevant part in CN101240181, the treated recovered grease and methanol or ethanol are heated to the temperature required by the reaction, then sodium hydroxide (accounting for 1% of the grease weight) or sodium methoxide is added as a catalyst, corresponding fatty acid methyl ester or ethyl ester is generated after a period of reaction, and the biodiesel is obtained after washing and drying.
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. The experimental procedures, which are not specified in the following examples, are generally determined according to national standards. If the corresponding national standard does not exist, the method is carried out according to the general international standard, the conventional condition or the condition recommended by the manufacturer.
Unless defined or otherwise indicated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In addition, any method and material similar or equivalent to those described may be used in the methods of the present invention.
The acidic ionic liquid is purchased from: china academy of sciences, lanzhou institute of chemical and physical
The clay oil content is determined according to the method of GB/T14488.1-2008 vegetable oil content determination.
Embodiment one:
taking 100 g of soybean oil decolorized spent bleaching clay and 1-butyl-3-methylimidazole dihydrogen phosphate (BmimH) 2 PO 4 ) 2.0 g of distilled water 300 g is placed in a 1L reaction kettle,heating to 180deg.C under stirring at 100rpm, stirring for 10 hr, cooling to 60deg.C, standing for 2 hr, sucking upper oil layer, filtering, and measuring its weight. 18.73 g of grease was obtained. The residual oil was measured after drying the deoiling spent bleaching clay. The waste clay residual oil is reduced from 20.39% to 0.38%. The recovery rate of the grease is 91.85 percent. The deoiling spent bleaching clay is washed by water and then dried in a baking oven at 105 ℃ for 1 hour, the water content of the spent bleaching clay is measured to be 8.98%, and the spent bleaching clay is crushed and then screened by a 200-mesh sieve, thus 75.36 g of regenerated bleaching clay is obtained. The decolorization ratio of the regenerated clay was measured by using the neutralized soybean oil, and the decolorization force of the regenerated clay was 96% of that of the fresh white clay.
Embodiment two:
taking 100 g of soybean oil decolorized spent bleaching clay and 1-butyl-3-methylimidazole dihydrogen phosphate (BmimH) 2 PO 4 ) 8.0 g of distilled water 250 g is placed in a 1L reaction kettle, the temperature is raised to 220 ℃ under the stirring condition of the rotating speed of 100rpm, the stirring is carried out for 12 hours, the temperature is reduced to 60 ℃, the temperature is kept still for 2 hours, the upper grease layer is sucked, and the weight of the grease is measured after filtration, so as to obtain 18.65 g of grease. The residual oil was measured after drying the deoiling spent bleaching clay. The waste clay residual oil is reduced from 20.39% to 0.26%. The recovery rate of the grease is 91.47 percent. The deoiling spent bleaching clay is washed by water and dried in a baking oven at 105 ℃ for 1 hour, the water content of the spent bleaching clay is measured to be 9.29%, and the spent bleaching clay is crushed and then screened by a 200-mesh sieve, thus 74.58 g of regenerated bleaching clay is obtained. The decolorization ratio of the regenerated clay was measured by using the neutralized soybean oil, and the decolorization force of the regenerated clay was 99% of that of the fresh white clay.
Embodiment III:
80 g of palm oil decolorized spent bleaching clay and 1-butyl-3-methylimidazole hydrogen phosphate (BmimHPO) are taken 4 ) 7.2 g of distilled water 240 g is placed in a 1L reaction kettle, the temperature is raised to 200 ℃ under the stirring condition of the rotating speed of 100rpm, the stirring is carried out for 15 hours, the temperature is reduced to 80 ℃, the heat is preserved and kept still for 2 hours, the upper grease layer is sucked, and the weight of the grease is measured after filtration, so as to obtain 18.69 g of grease. The residual oil was measured after drying the deoiling spent bleaching clay. The waste clay residual oil is reduced from 25.26% to 0.41%. The recovery rate of the grease is 92.49 percent. The deoiling spent bleaching clay is washed by water and dried in a baking oven at 105 ℃ for 1 hour, the water content of the spent bleaching clay is measured to be 8.42%, and the spent bleaching clay is crushed and then screened by a 200-mesh sieve, thus 54.83 g of regenerated bleaching clay is obtained. Determination of the regeneration Using neutralized Soybean oilThe decoloring rate of the clay and the decoloring force of the regenerated clay are 100% of that of the new white clay.
Embodiment four:
100 g of waste bleaching clay of corn oil and 3.0 g of 1-sulfobutyl-3-methylimidazole bisulfate (PSmimHSO) 4 ) And 300 g of tap water are placed in a 1L reaction kettle, the temperature is raised to 160 ℃ under the condition of stirring at 150rpm, the stirring is carried out for 13 hours, the temperature is reduced to 60 ℃, the reaction kettle is kept still for 2 hours, the upper grease layer is sucked, and the weight of the grease layer is measured after filtration, so that 20.46 g of grease is obtained. After the deoiling spent bleaching clay is dried, the residual oil is measured, the residual oil of the spent bleaching clay is reduced from 22.68% to 0.47%, and the oil recovery rate is 90.21%. The deoiling spent bleaching clay is washed by water and then dried in an oven at 105 ℃ for 1 hour, the water content of the spent bleaching clay is measured to be 7.95 percent, and the spent bleaching clay is crushed and then screened by a 200-mesh sieve to obtain 72.89 grams of regenerated bleaching clay. The decolorization ratio of the regenerated clay was measured by using the neutralized soybean oil, and the decolorization force of the regenerated clay was 95% of that of the fresh white clay.
Fifth embodiment:
100 g of waste bleaching clay of rice bran oil and 1-sulfobutyl-3-methylimidazole bisulfate (PSmimHSO) are taken 4 ) 2.5 g of distilled water 280 g is placed in a 1L reaction kettle, the temperature is raised to 190 ℃ under the condition of stirring at 120rpm, the stirring is carried out for 8 hours, the temperature is reduced to 60 ℃, the temperature is kept still for 2 hours, the upper grease layer is sucked, and after filtration, the weight is measured, thus obtaining 21.99 g of grease. After the deoiling spent bleaching clay is dried, the residual oil is measured, the residual oil of the spent bleaching clay is reduced from 23.84% to 0.42%, and the oil recovery rate is 92.24%. The deoiling spent bleaching clay is washed by water and then dried in an oven at 105 ℃ for 1 hour, the water content of the spent bleaching clay is measured to be 7.76%, and the spent bleaching clay is crushed and then screened by a 200-mesh sieve, so that 72.56 g of regenerated bleaching clay is obtained. The decolorization ratio of the regenerated clay was measured by using the neutralized soybean oil, and the decolorization force of the regenerated clay was 97% of that of the fresh white clay.
Example six:
50 g of soybean oil decolorized spent bleaching clay (BmimH 2 PO) is taken 4 ) 10.0 g of distilled water, 500 g of distilled water, placing the mixture into a 1L reaction kettle, heating to 140 ℃ under the stirring condition of the rotating speed of 100rpm, stirring for 20 hours, cooling to 60 ℃, standing for 2 hours, sucking an upper grease layer, filtering, and measuring the weight of the grease layer. Obtaining oilFat 9.40 g. The residual oil was measured after drying the deoiling spent bleaching clay. The waste clay residual oil is reduced from 20.39% to 0.36%. The recovery rate of the grease is 92.20 percent. The deoiling spent bleaching clay is washed by water and dried in a baking oven at 105 ℃ for 1 hour, the water content of the spent bleaching clay is measured to be 8.69 percent, and the spent bleaching clay is crushed and then screened by a 200-mesh sieve, thus obtaining 37.76 grams of regenerated bleaching clay. The decolorization ratio of the regenerated clay was measured by using the neutralized soybean oil, and the decolorization force of the regenerated clay was 98% of that of the fresh white clay.
Embodiment seven:
80 g of palm oil decolorized spent bleaching clay and 1-butyl-3-methylimidazole hydrogen phosphate (BmimHPO) are taken 4 ) 0.08 g of distilled water, 80 g of distilled water, placing the mixture into a 1L reaction kettle, heating to 300 ℃ under the stirring condition of the rotating speed of 100rpm, stirring for 1 hour, cooling to 80 ℃, keeping the temperature for 2 hours, sucking an upper grease layer, filtering, and measuring the weight of the grease layer to obtain 18.43 g of grease. The residual oil was measured after drying the deoiling spent bleaching clay. The waste clay residual oil is reduced from 25.26% to 0.19%. The recovery rate of the grease is 91.20 percent. The deoiling spent bleaching clay is washed by water and dried in a baking oven at 105 ℃ for 1 hour, the water content of the spent bleaching clay is measured to be 8.21%, and the spent bleaching clay is crushed and then screened by a 200-mesh sieve, thus 54.96 g of regenerated bleaching clay is obtained. The decolorization ratio of the regenerated clay was measured by using the neutralized soybean oil, and the decolorization force of the regenerated clay was 102% of that of the fresh white clay.
Comparative example one:
100 g of soybean oil decolorized 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 100rpm, the stirring is carried out for 20 hours, the temperature is reduced to 60 ℃, the reaction kettle is kept still for 2 hours, and no oil precipitation is observed on the upper layer. The treated spent bleaching clay was dried and its residual oil was measured. The spent bleaching clay residual oil is reduced from 20.39% to 20.28% with little change. The deoiling spent bleaching clay is filtered and dried in a baking oven at 105 ℃ for 1 hour, the water content of the spent bleaching clay is measured to be 8.98%, and the spent bleaching clay is crushed and sieved by a 200-mesh sieve to obtain 99.16 g of regenerated bleaching clay. The decolorization ratio of the regenerated clay was measured by using the neutralized soybean oil, and the decolorization force of the regenerated clay was 12% of that of the fresh white clay.
Comparative example two:
100 g of soybean oil decolorized waste carclazyte and 300 g of normal hexane are taken and placed in a 1L three-neck flask, the temperature is raised to 50 ℃, the rotating speed is 150rpm, the mixture is stirred for 10 hours, suction filtration is carried out, the filtrate is evaporated by a rotary evaporator, the normal hexane is recovered, and the weight of the recovered oil is measured, so that 18.58 g of oil is obtained. The residual oil was measured after drying the deoiling spent bleaching clay. The waste clay residual oil is reduced from 20.39% to 0.88%. The recovery rate of the oil was 91.12%. The deoiling spent bleaching clay is dried in a 105 ℃ oven for 1 hour, the water content of the spent bleaching clay is measured to be 5.63 percent, and the spent bleaching clay is crushed and then screened by a 200-mesh sieve to obtain 76.28 grams of regenerated bleaching clay. The decolorization ratio of the regenerated clay was measured by using the neutralized soybean oil, and the decolorization force of the regenerated clay was 8% of that of the fresh white clay.
Comparative example three:
100 g of corn oil decolorized waste clay, 300 g of tap water and 5 g of sodium hydroxide are taken, placed in a 1L reaction kettle, heated to 210 ℃ under the condition of stirring at 150rpm, stirred for 13 hours, cooled to 60 ℃, kept still for 2 hours, an upper grease layer is sucked, and the weight of the grease is measured after filtration, so that 14.25 g of grease is obtained. After the deoiling spent bleaching clay is dried, the residual oil is measured, the residual oil of the spent bleaching clay is reduced from 22.68% to 0.21%, and the oil recovery rate is 62.83%. The deoiling spent bleaching clay is dried in a 105 ℃ oven for 1 hour, the water content of the spent bleaching clay is measured to be 6.79%, and the spent bleaching clay is crushed and then screened by a 200-mesh sieve, so that 74.13 g of regenerated bleaching clay is obtained. The decolorization ratio of the regenerated clay was measured by using the neutralized soybean oil, and the decolorization force of the regenerated clay was 26% of that of the fresh white clay.
Comparative example four:
100 g of corn oil decolorized waste clay, 300 g of tap water and 5 g of sodium carbonate are taken, placed in a 1L reaction kettle, heated to 210 ℃ under the stirring condition of 150rpm, stirred for 13 hours, cooled to 60 ℃, kept still for 2 hours, an upper grease layer is sucked, and the weight of the grease is measured after filtration, so that 16.31 g of grease is obtained. After the deoiling spent bleaching clay is dried, the residual oil is measured, the residual oil of the spent bleaching clay is reduced from 22.68% to 1.12%, and the oil recovery rate is 71.91%. The deoiling spent bleaching clay is dried in a 105 ℃ oven for 1 hour, the water content of the spent bleaching clay is measured to be 8.22 percent, and the spent bleaching clay is crushed and then screened by a 200-mesh sieve, so that 72.08 grams of regenerated bleaching clay is obtained. The decolorization ratio of the regenerated clay was measured by using the neutralized soybean oil, and the decolorization force of the regenerated clay was 45% of that of the fresh white clay.
Comparative example five:
taking 100 g of soybean oil decolorized waste carclazyte, 300 g of distilled water and 5 g of potassium hydroxide, placing the waste carclazyte into a 1L reaction kettle, heating to 200 ℃ under the condition of stirring at 150rpm, stirring for 15 hours, cooling to 60 ℃, standing for 2 hours, sucking an upper grease layer, filtering, and measuring the weight of the grease layer to obtain 14.21 g of grease. The waste clay residual oil is reduced from 20.39% to 0.51%. The recovery rate of the oil was 69.69%. The deoiling spent bleaching clay is dried in a 105 ℃ oven for 1 hour, the water content of the spent bleaching clay is measured to be 7.72 percent, and the spent bleaching clay is crushed and then screened by a 200-mesh sieve to obtain 75.10 grams of regenerated bleaching clay. The decolorization ratio of the regenerated clay was measured by using the neutralized soybean oil, and the decolorization force of the regenerated clay was 12% of that of the fresh white 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, placed in a 1L reaction kettle, heated to 200 ℃ under the stirring condition of 150rpm, stirred for 15 hours, cooled to 60 ℃, and kept still for 2 hours, an upper grease layer is sucked, and after filtration, the weight of the grease layer is measured, thus obtaining 17.21 g of grease. The waste clay residual oil is reduced from 20.39% to 1.89%. The recovery rate of the grease is 84.40 percent. The deoiling spent bleaching clay is dried in a 105 ℃ oven for 1 hour, the water content of the spent bleaching clay is measured to be 6.77 percent, and the spent bleaching clay is crushed and then screened by a 200-mesh sieve to obtain 73.26 grams of regenerated bleaching clay. The decolorization ratio of the regenerated clay was measured with the neutralized soybean oil, and the decolorization force of the regenerated clay was 79% of that of the fresh white clay.
Comparative example seven:
100 g of soybean oil decolorized waste carclazyte, 300 g of distilled water and 8 g of phosphoric acid are taken, placed in a 1L reaction kettle, heated to 200 ℃ under the condition of stirring at 150rpm, stirred for 15 hours, cooled to 60 ℃, and kept still for 2 hours, an upper grease layer is sucked, and the weight of the grease layer is measured after filtration, so as to obtain 17.01 g of grease. The waste clay residual oil is reduced from 20.39% to 1.62%. The recovery rate of the grease is 83.42 percent. The deoiling spent bleaching clay is dried in a 105 ℃ oven for 1 hour, the water content of the spent bleaching clay is measured to be 6.77 percent, and the spent bleaching clay is crushed and then screened by a 200-mesh sieve to obtain 73.26 grams of regenerated bleaching clay. The decolorization ratio of the regenerated clay was measured by using the neutralized soybean oil, and the decolorization force of the regenerated clay was 72% of that of the fresh white clay.
Comparative example eight:
taking 100 g of soybean oil decolorized waste carclazyte, 300 g of distilled water and 8 g of nitric acid, placing the waste carclazyte into a 1L reaction kettle, heating to 210 ℃ under the stirring condition of the rotating speed of 150rpm, stirring for 13 hours, cooling to 60 ℃, standing for 2 hours, sucking an upper grease layer, filtering, and measuring the weight of the grease layer to obtain 16.12 g of grease. The waste clay residual oil is reduced from 20.39% to 2.32%. The recovery rate of the grease is 79.06%. The deoiling spent bleaching clay is dried in a 105 ℃ oven for 1 hour, the water content of the spent bleaching clay is measured to be 7.12 percent, and the spent bleaching clay is crushed and then screened by a 200-mesh sieve to obtain 73.87 grams of regenerated bleaching clay. The decolorization ratio of the regenerated clay was measured by using the neutralized soybean oil, and the decolorization force of the regenerated clay was 69% of that of the fresh white clay.
The differences between the examples and the comparative examples are summarized in the following table:
the table shows that the method of the invention can not only effectively extract the grease from the waste clay, but also can recycle the grease-extracted deoiling clay as fresh clay after simple washing, drying and crushing. The process can realize the recycling of the carclazyte while extracting the grease, reduce the generation of solid waste in the grease refining process and greatly reduce the refining cost.
The foregoing description is only illustrative of the preferred embodiments of the present invention and is not intended to limit the scope of the invention, which is defined broadly in the appended claims, and any person skilled in the art to which the invention pertains will readily appreciate that many modifications, including those that fall within the metes and bounds of the claims, or equivalence of such metes and bounds thereof.
Claims (14)
1. A method for regenerating spent bleaching clay, which is characterized by comprising the steps of contacting 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;
wherein the contact mode is to carry out thermal reaction on the waste clay mixture containing waste clay, acidic ionic liquid and water; the thermal reaction temperature is 140-300 ℃;
the acidic ionic liquid comprises any one or a combination of more of chloroaluminate acidic ionic liquid, carboxyl acidic ionic liquid, sulfonic acidic ionic liquid, benzenesulfonic acidic ionic liquid, imidazole acidic ionic liquid, amide acidic ionic liquid, choline acidic ionic liquid, phenylimidazole salt acidic ionic liquid and triethylamine double acidic ionic liquid;
the thermal reaction time is 1-20h;
the step of separating the spent bleaching clay mixture to obtain regenerated bleaching clay specifically comprises the following characteristics:
solid-liquid separation is carried out on the waste clay mixture to obtain a waste white clay phase; and/or
Washing and/or drying the spent bleaching clay phase to obtain regenerated bleaching clay.
2. A method for recovering grease from spent bleaching clay, which is characterized by comprising the steps of contacting acidic ionic liquid with spent bleaching clay to obtain a spent bleaching clay mixture; and separating the spent bleaching clay mixture to obtain recovered grease;
wherein the contact mode is to carry out thermal reaction on the waste clay mixture containing waste clay, acidic ionic liquid and water; the thermal reaction temperature is 140-300 ℃;
the acidic ionic liquid comprises any one or a combination of more of chloroaluminate acidic ionic liquid, carboxyl acidic ionic liquid, sulfonic acidic ionic liquid, benzenesulfonic acidic ionic liquid, imidazole acidic ionic liquid, amide acidic ionic liquid, choline acidic ionic liquid, phenylimidazole salt acidic ionic liquid and triethylamine double acidic ionic liquid;
the thermal reaction time is 1-20h;
the step of separating the spent bleaching clay mixture to obtain grease specifically comprises the following characteristics:
solid-liquid separation is carried out on the spent bleaching clay mixture to obtain an oil phase; and/or
And washing and/or drying the grease phase to obtain the recovered grease.
3. The method of claim 1 or 2, wherein the thermal reaction temperature is 150 ℃ to 280 ℃.
4. The method of claim 1 or 2, wherein the thermal reaction temperature is 160 ℃ to 220 ℃.
5. The method of claim 1 or 2, wherein the thermal reaction time is 2 to 15 hours.
6. The method of claim 1 or 2, wherein the thermal reaction time is 10 to 15 hours.
7. The method of claim 1 or 2, comprising one or more of the following features:
1) The oil content of the spent bleaching clay is 10-50wt%;
2) The waste clay mixture contains water, and the weight of the water is 1-10 times of that of the waste clay;
3) The weight of the acidic ionic liquid in the spent bleaching clay mixture is 0.1-20% of the weight of the spent bleaching clay.
8. The method of claim 7, wherein the weight of water is 2-5 times the weight of spent bleaching clay.
9. The method of claim 7, wherein the weight of water is 2-3 times the weight of spent bleaching clay.
10. The process of claim 7 wherein the weight of acidic ionic liquid in the spent bleaching clay mixture is from 0.5% to 10% of the weight of spent bleaching clay.
11. The method of claim 1 or 2, further comprising the step of cooling the resulting mixture prior to the solid-liquid separation.
12. The method of claim 11, wherein the step of reducing the temperature reduces the temperature to below 100 ℃.
13. A regenerated clay obtained by the process of claim 1.
14. The recovered oil obtained by the method of claim 2.
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| CN115353933B (en) * | 2022-10-19 | 2023-03-17 | 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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