CN113788876B - Method for extracting protein from chrome tanning scraps based on ionic liquid aqueous two-phase system - Google Patents
Method for extracting protein from chrome tanning scraps based on ionic liquid aqueous two-phase system Download PDFInfo
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- CN113788876B CN113788876B CN202111119858.6A CN202111119858A CN113788876B CN 113788876 B CN113788876 B CN 113788876B CN 202111119858 A CN202111119858 A CN 202111119858A CN 113788876 B CN113788876 B CN 113788876B
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 102000004169 proteins and genes Human genes 0.000 title claims abstract description 93
- 108090000623 proteins and genes Proteins 0.000 title claims abstract description 93
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000011651 chromium Substances 0.000 claims abstract description 42
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 38
- 239000002738 chelating agent Substances 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 5
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 28
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 10
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- AVTYONGGKAJVTE-OLXYHTOASA-L potassium L-tartrate Chemical group [K+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O AVTYONGGKAJVTE-OLXYHTOASA-L 0.000 claims description 8
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 claims description 8
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims description 8
- 235000011054 acetic acid Nutrition 0.000 claims description 7
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 5
- 235000011009 potassium phosphates Nutrition 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 229940074439 potassium sodium tartrate Drugs 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 229910001430 chromium ion Inorganic materials 0.000 claims description 2
- 238000004064 recycling Methods 0.000 abstract description 9
- 238000010438 heat treatment Methods 0.000 abstract description 6
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 3
- 239000003344 environmental pollutant Substances 0.000 abstract description 2
- 231100000719 pollutant Toxicity 0.000 abstract description 2
- 239000012071 phase Substances 0.000 description 37
- 239000000047 product Substances 0.000 description 34
- 239000007788 liquid Substances 0.000 description 23
- 239000000203 mixture Substances 0.000 description 14
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 239000003513 alkali Substances 0.000 description 9
- 230000000887 hydrating effect Effects 0.000 description 9
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 9
- 102000008186 Collagen Human genes 0.000 description 6
- 108010035532 Collagen Proteins 0.000 description 6
- 229920001436 collagen Polymers 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000012467 final product Substances 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 239000010985 leather Substances 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 229910021642 ultra pure water Inorganic materials 0.000 description 6
- 239000012498 ultrapure water Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 229940095064 tartrate Drugs 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 4
- 238000005191 phase separation Methods 0.000 description 4
- -1 phosphate anions Chemical class 0.000 description 4
- 239000001476 sodium potassium tartrate Substances 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical group OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 150000001844 chromium Chemical class 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- UOFGSWVZMUXXIY-UHFFFAOYSA-N 1,5-Diphenyl-3-thiocarbazone Chemical compound C=1C=CC=CC=1N=NC(=S)NNC1=CC=CC=C1 UOFGSWVZMUXXIY-UHFFFAOYSA-N 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 238000001311 chemical methods and process Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000001472 potassium tartrate Substances 0.000 description 2
- 229940111695 potassium tartrate Drugs 0.000 description 2
- 235000011005 potassium tartrates Nutrition 0.000 description 2
- 238000000751 protein extraction Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- IAZSXUOKBPGUMV-UHFFFAOYSA-N 1-butyl-3-methyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CCCC[NH+]1CN(C)C=C1 IAZSXUOKBPGUMV-UHFFFAOYSA-N 0.000 description 1
- ZXLOSLWIGFGPIU-UHFFFAOYSA-N 1-ethyl-3-methyl-1,2-dihydroimidazol-1-ium;acetate Chemical compound CC(O)=O.CCN1CN(C)C=C1 ZXLOSLWIGFGPIU-UHFFFAOYSA-N 0.000 description 1
- XUHHZNLAPUWRHH-UHFFFAOYSA-N 3-butyl-1-methyl-1,2-dihydroimidazol-1-ium;methanesulfonate Chemical compound CS(O)(=O)=O.CCCCN1CN(C)C=C1 XUHHZNLAPUWRHH-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- MCZDHTKJGDCTAE-UHFFFAOYSA-M tetrabutylazanium;acetate Chemical compound CC([O-])=O.CCCC[N+](CCCC)(CCCC)CCCC MCZDHTKJGDCTAE-UHFFFAOYSA-M 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07K—PEPTIDES
- C07K1/00—General methods for the preparation of peptides, i.e. processes for the organic chemical preparation of peptides or proteins of any length
- C07K1/14—Extraction; Separation; Purification
- C07K1/145—Extraction; Separation; Purification by extraction or solubilisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07K—PEPTIDES
- C07K1/00—General methods for the preparation of peptides, i.e. processes for the organic chemical preparation of peptides or proteins of any length
- C07K1/14—Extraction; Separation; Purification
- C07K1/30—Extraction; Separation; Purification by precipitation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Biophysics (AREA)
- Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Medicinal Chemistry (AREA)
- Molecular Biology (AREA)
- Proteomics, Peptides & Aminoacids (AREA)
- Analytical Chemistry (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention relates to a method for extracting proteins from chrome tanning scraps based on an ionic liquid aqueous two-phase system, and belongs to the technical field of recycling of the chrome tanning scraps. Adding hydrophilic ionic liquid, chelating agent and water into chrome tanning scraps, and fully and uniformly mixing to obtain a two-phase layered solution; wherein the upper phase is an ionic liquid and protein enrichment phase, and the lower phase is a chromium and chelating agent enrichment phase; separating the two-phase layered solution, adding protein precipitant into the upper phase separator to precipitate protein in the upper phase separator, and removing chromium from the chrome tanning scraps to extract protein. The method can efficiently and effectively extract the protein product with the heavy metal pollutant content less than 10mg/kg from the chrome tanning scraps, and the yield is more than 60 percent, and realizes the high-valued, harmless and recycling utilization of the chrome tanning scraps under the green conditions of no volatile organic matters and no high-temperature heating.
Description
Technical Field
The invention belongs to the technical field of recycling of chrome tanning scraps, and in particular relates to a method for extracting proteins from chrome tanning scraps based on an ionic liquid aqueous two-phase system.
Background
The annual yield of leather in China is the first in the world, and at present, the technology mainly applied to the production of leather in China is a chrome tanning method, namely tanning treatment is carried out on the leather by using a large amount of trivalent chromium salt, so that the leather becomes tough and soft, and becomes leather. Although the method is quick and effective and the produced leather products have good quality, a large amount of solid waste with high chromium content is generated in the tanning process, namely chrome tanning scraps, the chromium content of the chrome tanning scraps is 2 to 3 percent and is far more than the limit value of chromium heavy metal specified in the related waste standard. The chrome tanning scraps are belonged to dangerous wastes, a large amount of chrome tanning scraps can be generated each year in the China tanning industry, and the requirements of harmless recycling treatment and secondary pollution cannot be caused in the treatment process are increasing. The current industrial technology for treating the chrome tanning scraps is acid/alkali hydrolysis, and the methods are that firstly, acid or alkali solution is used for carrying out long-time soaking pretreatment on the chrome tanning scraps, and then the chrome tanning scraps are heated under the acid/alkali condition to hydrolyze, so that chromium elements crosslinked with collagen in the chrome tanning scraps can be separated. But the method can not separate protein products with chromium content less than 10mg/kg, and a large amount of acid/alkali wastewater is easy to generate in the treatment process, thus easily causing secondary pollution to the environment. The hydrolysis process in the method also needs to heat the hydrolysis liquid for a long time, and the treatment process has high energy consumption and is not friendly to the environment.
Disclosure of Invention
The invention solves the technical problems that the chromium content of the protein separated from the chrome tanning scraps is large, and a large amount of acid/alkali wastewater is easy to generate in the treatment process, thereby causing pollution in the prior art. Aiming at the demands of the prior art and the defects of the prior art, the invention provides a chromium salt and protein separation technology based on an ionic liquid aqueous two-phase system, which can separate collagen and chromium salt at room temperature in one step and recover protein products with the chromium content less than 10mg/kg. Since the method does not use volatile organic solvents and does not need high-temperature heating, industrial waste gas is hardly generated; since the method does not require heating, no expensive high temperature reaction equipment is required; because the ionic liquid-based two-aqueous phase separation technology is innovatively used in the scheme, compared with the traditional technology, the technology can achieve the effect of quickly and efficiently separating chromium from collagen.
According to the object of the present invention, there is provided a method for the dechromization extraction of proteins from chrome tanning scraps based on an ionic liquid aqueous two-phase system, comprising the following steps:
(1) Adding hydrophilic ionic liquid, chelating agent and water into chrome tanning scraps, and fully and uniformly mixing to obtain a two-phase layered solution; wherein the upper phase is a hydrophilic ionic liquid and protein enrichment phase, and the lower phase is a chromium ion and chelating agent enrichment phase; the mass ratio of the chelating agent to the water is more than or equal to 5:6, and the mass ratio of the chrome tanning scraps to the hydrophilic ionic liquid is less than or equal to 1:4;
(2) Separating the two-phase layered solution obtained in the step (1), adding a protein precipitant into the upper phase separator to precipitate protein in the upper phase separator, namely, removing chromium from the chrome tanning scraps and extracting the protein.
Preferably, after the protein in the upper phase separator is precipitated, a mixed solution of the hydrophilic ionic liquid and the protein precipitant is left, and the mixed solution is subjected to evaporation separation, so that the protein precipitant and the hydrophilic ionic liquid are separated, and the separated hydrophilic ionic liquid can be recycled in the step (1).
Preferably, the hydrophilic ionic liquid is a quaternary ammonium salt ionic liquid or an imidazole ionic liquid.
Preferably, the quaternary ammonium salt ionic liquid is tetrabutylammonium hydroxide, tetrabutylammonium chloride or tetrabutylammonium acetate; the imidazole ionic liquid is 1-butyl-3-methylimidazole chloride, 1-ethyl-3-methylimidazole acetate or 1-butyl-3-methylimidazole mesylate.
Preferably, the chelating agent is tartrate or ethylenediamine tetraacetic acid.
Preferably, the tartrate is potassium L-tartrate or sodium potassium tartrate.
Preferably, the protein precipitant is at least one of acetone, ethanol, methanol, acetic acid, formic acid, and ammonium sulfate.
Preferably, in step (1), the method further comprises adding a hydrating agent to the chrome tanning crumb.
Preferably, the hydrating agent is phosphate, sodium hydroxide, potassium hydroxide, or dithizone.
Preferably, in the step (1), the fully and uniformly mixed mode is stirring, and the stirring time is more than 2.5h.
In general, compared with the prior art, the above technical solution conceived by the present invention mainly has the following technical advantages:
(1) The acid/alkali hydrolysis method used for treating the chrome tanning scraps at present can not obtain a protein product with the chromium content of less than 10mg/kg, and the invention can obtain the protein product with the chromium content of less than 10mg/kg on the premise of not producing highly toxic hexavalent chromium, thereby filling the blank in the harmless and recycling fields of the chrome tanning scraps to a certain extent. The technical scheme has the advantages of simple operation flow, no need of heating treatment, capability of recycling the reagent in theory, environment friendliness, large scale production potential and huge potential social benefit, and meets the requirements of the green chemical process.
(2) At present, the traditional process for chrome tanning scraps cannot separate protein products with the chromium content less than 10mg/kg purity by an acid/alkali hydrolysis method, and the subsequent application of the products is greatly limited. According to the invention, however, collagen in chrome tanning scraps can be dissolved by an ionic liquid-based two-aqueous phase system, chromium is chelated, and finally pollutants are thoroughly removed by natural phase separation layering, so that the protein product can reach a chromium content of less than 10mg/kg.
(3) When lyophilic ions (e.g., phosphate anions, tartrate anions) are added to the aqueous chrome tannage solution, water molecules near these ions will be in an electrically contracted state, the hydrogen bond network of water will be enhanced at this stage, and the hydrogen bond network of water will not form cavities around bulky organic cations, such as tetrabutylammonium, imidazole cations, etc., so that a two-aqueous-phase system can be effectively formed. Because in the system, the lower phase is preferably a tartrate-rich phase, and the tartrate anions have strong chelating ability for trivalent chromium, trivalent chromium can be effectively removed from the macromolecular side chains of the protein and enter the lower phase.
(4) The reason why the mass ratio of the chelating agent to the water is more than or equal to 5:6 and the mass of the chrome tanning scraps is less than or equal to 30% of the mass of the ionic liquid is that: the greater the chelating agent concentration, the higher the chelating agent ratio will partition to the lower phase when the concentration reaches 5: when the ratio of the mass of the chrome tanning scraps to the mass of the ionic liquid is less than or equal to 1:4, more than 99.9% of chelating agent enters the lower phase, so that the trivalent chromium concentration of the upper phase can be maintained at an extremely low level, and the aim of separating chromium elements from proteins is fulfilled, because the ionic liquid can effectively and rapidly dissolve the chrome tanning scraps only when the ratio is less than 1:4.
(5) At present, a large amount of acid/alkaline wastewater is generated after the hydrolysis step aiming at the traditional process of chrome tanning scraps, the chemical wastewater is easy to cause secondary pollution to the environment, and the subsequent treatment steps are complicated and cannot be recovered. The ionic liquid and the protein precipitant used in the invention can be recovered through the subsequent separation and purification steps and recycled, thereby avoiding the discharge of a large amount of industrial wastewater.
(6) When the traditional alkaline hydrolysis method and the acid hydrolysis method are used for treating chrome tanning scraps, the optimal chromium removal effect is usually achieved through long-time heating treatment, but the high-temperature heating treatment is carried out under the acid/alkali condition for a long time, so that the reactor has strong corrosion resistance requirements, and the problems of excessively high energy consumption and secondary pollution to the environment caused by waste gas are caused. The ionic liquid used by the invention has the characteristics of low vapor pressure and non-volatilization, and the technical scheme can be carried out at room temperature, so that the energy consumption is low, the waste gas can not be discharged, the environment is friendly, and the requirements of a green chemical process are met.
Drawings
Fig. 1 is a schematic diagram of a main process flow for chromium removal and protein extraction based on an ionic liquid aqueous two-phase system.
FIG. 2 shows the variation of chromium content of the protein product with prolonged stirring time.
FIG. 3 shows the difference in chromium content of the protein product before and after the addition of the hydrating agent.
FIG. 4 shows the amino acid profile of the protein product obtained in example 2.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
Fig. 1 is a schematic diagram of a main process flow for chromium removal and protein extraction based on an ionic liquid aqueous two-phase system. The invention relates to a method for extracting protein based on ionic liquid double water phase system chromium removal, which specifically comprises the following steps:
(1) Adding the ionic liquid, water, the chelating agent and the chrome tanning scraps into a mixing stirrer, stirring for 6 to 10 hours at a certain temperature, stopping stirring to naturally form two-phase layering, wherein the upper layer is an ionic liquid and collagen enrichment phase, and the lower layer is a chromium and chelating agent phase; the ionic liquid comprises but is not limited to quaternary ammonium salt ionic liquid and imidazole ionic liquid which have solubility property on protein;
(2) Separating the two-phase layered solution obtained in the last step, adding a protein precipitant into the upper phase separator to precipitate protein, and separating the mixture to obtain a mixture of the ionic liquid and the protein precipitant, wherein the solid is a protein product and the liquid is an ionic liquid; the protein precipitant comprises one or more of acetone, ethanol, methanol, acetic acid, formic acid, ammonium sulfate and other reagents, and is characterized in that the protein precipitant can cause the protein in the ionic liquid to precipitate;
(3) And (3) carrying out evaporation separation operation on the mixed liquid of the ionic liquid and the protein precipitant obtained in the last step, separating the protein precipitant from the ionic liquid, and recycling the reagent.
Preferably, the step (1) further comprises adding a hydrating agent, including but not limited to at least one of phosphates, alkali compounds, dithizone and other reagents, which can promote the formation of natural phase separation and delamination phenomenon with the ionic liquid.
Example 1
The invention discloses a method for extracting proteins from chrome tanning scraps by removing chromium based on an ionic liquid aqueous two-phase system, which comprises the following steps:
(1) Tetrabutylammonium hydroxide (a quaternary ammonium salt ionic liquid), chrome tanning scraps, and L-potassium tartrate (with the functions of a chelating agent and a hydrating agent) are mixed with ultrapure water, and the proportion is tetrabutylammonium hydroxide: water: potassium L-tartrate: chrome tanning crumb = 4:6:5:1, a step of;
(2) Stirring the mixture fully for 8 hours at 30 ℃;
(3) Standing the mixture until natural split phases are layered into an upper layer and a lower layer, wherein the upper layer is light yellow clear liquid, the lower layer is dark green clear liquid, and taking the light yellow clear liquid of the upper layer for next operation;
(4) Adding acetone and absolute ethanol mixed solution (protein precipitant) into the upper pale yellow clear solution to obtain protein product precipitate;
(5) Filtering and washing the protein product for three times, and drying for 2 hours at 60 ℃ to obtain a final product;
(6) And (3) distilling and separating the mixed liquid of the ionic liquid and the protein precipitant, distilling the protein precipitant into gas at 80 ℃, condensing and recovering to obtain purified ionic liquid and purified protein precipitant, and recycling.
(7) The protein product was tested by ICP-OES and the Cr content was 3.33mg/kg.
Example 2
The invention discloses a method for extracting proteins from chrome tanning scraps by removing chromium based on an ionic liquid aqueous two-phase system, which comprises the following steps:
(1) Tetrabutylammonium hydroxide (a quaternary ammonium salt ionic liquid), chrome tanning scraps, potassium sodium tartrate (chelating agent), potassium phosphate (hydrating agent) and ultrapure water are mixed, wherein the proportion is tetrabutylammonium hydroxide: water: sodium potassium tartrate: potassium phosphate: chrome tanning crumb = 4:6:2:1:1, a step of;
(2) Stirring the mixture fully for 8 hours at 30 ℃;
(3) Standing the mixture until natural split phases are layered into an upper layer and a lower layer, wherein the upper layer is light yellow clear liquid, the lower layer is dark green clear liquid, and taking the light yellow clear liquid of the upper layer for next operation;
(4) Adding acetic acid and ethanol mixed solution (protein precipitant) into the supernatant to obtain protein product precipitate;
(5) And (3) filtering and washing the protein product for three times, and drying the protein product for 2 hours at the temperature of 60 ℃ to obtain a final product.
(6) The protein product was tested by ICP-OES and the Cr content was 1.74mg/kg.
FIG. 4 shows the amino acid profile of the protein product obtained in example 2, demonstrating that the major components of the product are proteins.
Example 3
The invention discloses a method for extracting proteins from chrome tanning scraps by removing chromium based on an ionic liquid aqueous two-phase system, which comprises the following steps:
(1) Tetrabutylammonium hydroxide (a quaternary ammonium salt ionic liquid), chrome tanning scraps, and L-potassium tartrate (with the functions of a chelating agent and a hydrating agent) are mixed with ultrapure water, and the proportion is tetrabutylammonium hydroxide: water: potassium L-tartrate: chrome tanning crumb = 4:6:5:1, a step of;
(2) Stirring the mixture fully for 8 hours at 30 ℃;
(3) Standing the mixture until natural split phases are layered into an upper layer and a lower layer, wherein the upper layer is light yellow clear liquid, the lower layer is dark green clear liquid, and taking the light yellow clear liquid of the upper layer for next operation;
(4) Adding acetone and absolute ethanol mixed solution (protein precipitant) into the upper pale yellow clear solution to obtain protein product precipitate;
(5) Filtering and washing the protein product for three times, and drying for 2 hours at 60 ℃ to obtain a final product;
(6) And (3) distilling and separating the mixed liquid of the ionic liquid and the protein precipitant, distilling the protein precipitant into gas at 80 ℃, condensing and recovering to obtain purified ionic liquid and purified protein precipitant, and recycling.
(7) The protein product was tested by ICP-OES and the Cr content was 6.11mg/kg.
Example 4
The invention discloses a method for extracting proteins from chrome tanning scraps by removing chromium based on an ionic liquid aqueous two-phase system, which comprises the following steps:
(1) Tetrabutylammonium hydroxide (a quaternary ammonium salt ionic liquid), chrome tanning scraps, potassium tartrate (chelating agent) and ultrapure water are mixed, wherein the proportion is tetrabutylammonium hydroxide: water: potassium tartrate: chrome tanning crumb = 6:6:5:1, a step of;
(2) Stirring the mixture fully for 8 hours at 30 ℃;
(3) Standing the mixture until natural split phases are layered into an upper layer and a lower layer, wherein the upper layer is light yellow clear liquid, the lower layer is dark green clear liquid, and taking the light yellow clear liquid of the upper layer for next operation;
(4) Adding acetic acid and ethanol mixed solution (protein precipitant) into the supernatant to obtain protein product precipitate;
(5) And (3) filtering and washing the protein product for three times, and drying the protein product for 2 hours at the temperature of 60 ℃ to obtain a final product.
(6) The protein product was tested by ICP-OES and the Cr content was 5.32mg/kg.
Comparative example 1
This example is a comparative experiment conducted to demonstrate the necessity of agitation time for chromium removal, and is specifically described in the following embodiments:
(1) Tetrabutylammonium hydroxide (a quaternary ammonium salt ionic liquid), chrome tanning scraps, potassium sodium tartrate (chelating agent), potassium phosphate (hydrating agent) and ultrapure water are mixed, wherein the proportion is tetrabutylammonium hydroxide: water: sodium potassium tartrate: potassium phosphate: chrome tanning crumb = 4:6:2:1:1, a step of;
(2) Fully stirring the mixture at 30 ℃ for 1h, 2.5h and 4h;
(3) Standing the mixture until natural split phases are layered into an upper layer and a lower layer, wherein the upper layer is light yellow clear liquid, the lower layer is dark green clear liquid, and taking the light yellow clear liquid of the upper layer for next operation;
(4) Adding acetic acid and ethanol mixed solution (protein precipitant) into the supernatant to obtain protein product precipitate;
(5) Filtering and washing the protein product for three times, and drying for 2 hours at 60 ℃ to obtain a final product;
(6) The comparative example the comparative results are shown in fig. 2, comparative example 1, and demonstrate that chromium crosslinked with collagen cannot be completely sequestered and removed when the reaction time is insufficient.
Comparative example 2
This example is a comparative experiment conducted to demonstrate the necessity of a hydration agent, or the use of a sufficient amount of a chelating agent to replace the hydration agent for chromium removal, and is specifically described as follows:
(1) Tetrabutylammonium hydroxide (a quaternary ammonium salt ionic liquid), chrome tanning scraps, potassium sodium tartrate (chelating agent) and ultrapure water are mixed, wherein the proportion is tetrabutylammonium hydroxide: water: sodium potassium tartrate: chrome tanning crumb = 4:6:2:1, fully stirring the mixture at 30 ℃ for 1h, 2.5h and 4h;
(2) Standing the mixture until natural split phases are layered into an upper layer and a lower layer, wherein the upper layer is light yellow clear liquid, the lower layer is dark green clear liquid, and taking the light yellow clear liquid of the upper layer for next operation;
(3) Adding acetic acid and ethanol mixed solution (protein precipitant) into the supernatant to obtain protein product precipitate;
(4) Filtering and washing the protein product for three times, and drying for 2 hours at 60 ℃ to obtain a final product;
(5) The comparative example the comparative results are shown in FIG. 3 and comparative example 2, and demonstrate that incomplete phase separation results in chromium entering the protein product and failure of purification when no hydrating agent is added and the chelating agent is not added in sufficient amounts.
The heavy metal measuring method comprises the following steps: the chromium content in the protein product in the technical scheme is detected according to the determination method in GB5009.123-2014 determination of chromium in food safety national Standard food.
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (4)
1. The method for extracting the protein from the chrome tanning scraps by the double water phase system based on the ionic liquid is characterized by comprising the following steps of:
(1) Adding hydrophilic ionic liquid, chelating agent and water into chrome tanning scraps, and fully and uniformly mixing to obtain a two-phase layered solution; wherein the upper phase is a hydrophilic ionic liquid and protein enrichment phase, and the lower phase is a chromium ion and chelating agent enrichment phase; the mass ratio of the chelating agent to the water is more than or equal to 5:6, and the mass ratio of the chrome tanning scraps to the hydrophilic ionic liquid is less than or equal to 1:4;
the hydrophilic ionic liquid is tetrabutylammonium hydroxide;
the chelating agent is L-potassium tartrate or potassium sodium tartrate, and the water agent potassium phosphate is added at the same time;
(2) Separating the two-phase layered solution obtained in the step (1), adding a protein precipitant into the upper phase separator to precipitate protein in the upper phase separator, namely, removing chromium from the chrome tanning scraps and extracting the protein.
2. The method for extracting proteins from chrome tanning scraps based on an ionic liquid aqueous two-phase system according to claim 1, wherein after proteins in the upper phase separator are precipitated, a mixed solution of hydrophilic ionic liquid and protein precipitant is left, the mixed solution is subjected to evaporation separation, the protein precipitant and the hydrophilic ionic liquid are separated, and the separated hydrophilic ionic liquid can be recycled in the step (1).
3. The method for dechroming and extracting proteins from chrome tanning scraps based on an ionic liquid aqueous two-phase system according to claim 1, wherein the protein precipitant is at least one of acetone, ethanol, methanol, acetic acid, formic acid and ammonium sulfate.
4. The method for dechroming and extracting proteins from chrome tanning scraps based on an ionic liquid aqueous two phase system according to claim 1, wherein in the step (1), the fully uniform mixing mode is stirring, and the stirring time is more than 2.5h.
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