CN116808502B - Preparation and application of chromium-removing ammonia-reducing agent for chromium-containing collagen liquid extracted from waste leather scraps - Google Patents
Preparation and application of chromium-removing ammonia-reducing agent for chromium-containing collagen liquid extracted from waste leather scraps Download PDFInfo
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- CN116808502B CN116808502B CN202310781999.7A CN202310781999A CN116808502B CN 116808502 B CN116808502 B CN 116808502B CN 202310781999 A CN202310781999 A CN 202310781999A CN 116808502 B CN116808502 B CN 116808502B
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- chromium
- solution
- ammonia
- stirring
- acid
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 135
- 239000011651 chromium Substances 0.000 title claims abstract description 135
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 122
- 102000008186 Collagen Human genes 0.000 title claims abstract description 78
- 108010035532 Collagen Proteins 0.000 title claims abstract description 78
- 229920001436 collagen Polymers 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 46
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 18
- 239000007788 liquid Substances 0.000 title claims description 25
- 239000010985 leather Substances 0.000 title abstract description 44
- 239000002699 waste material Substances 0.000 title abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 115
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 103
- 238000000034 method Methods 0.000 claims abstract description 56
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 51
- 229910001430 chromium ion Inorganic materials 0.000 claims abstract description 37
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000001179 sorption measurement Methods 0.000 claims abstract description 30
- 239000000696 magnetic material Substances 0.000 claims abstract description 28
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000011282 treatment Methods 0.000 claims abstract description 23
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 20
- 239000010457 zeolite Substances 0.000 claims abstract description 20
- 238000000576 coating method Methods 0.000 claims abstract description 17
- 239000011248 coating agent Substances 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 14
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 8
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 143
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 93
- 238000003756 stirring Methods 0.000 claims description 92
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 75
- 239000008367 deionised water Substances 0.000 claims description 60
- 229910021641 deionized water Inorganic materials 0.000 claims description 60
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 45
- 238000001035 drying Methods 0.000 claims description 45
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 44
- 239000000047 product Substances 0.000 claims description 39
- 238000005406 washing Methods 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 34
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 30
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 28
- 239000002253 acid Substances 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 23
- 239000008188 pellet Substances 0.000 claims description 23
- -1 polytetrafluoroethylene Polymers 0.000 claims description 22
- 238000001914 filtration Methods 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 21
- 238000000926 separation method Methods 0.000 claims description 21
- VBZOUUJVGADJBK-UHFFFAOYSA-N 2-bromopropanedioic acid Chemical compound OC(=O)C(Br)C(O)=O VBZOUUJVGADJBK-UHFFFAOYSA-N 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 20
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 20
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 20
- 229910052794 bromium Inorganic materials 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 230000004913 activation Effects 0.000 claims description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 14
- 230000000694 effects Effects 0.000 claims description 12
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 230000007935 neutral effect Effects 0.000 claims description 11
- 238000004062 sedimentation Methods 0.000 claims description 11
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 10
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 10
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 10
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 8
- 239000000292 calcium oxide Substances 0.000 claims description 8
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 8
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 7
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 7
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 7
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052622 kaolinite Inorganic materials 0.000 claims description 7
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910021389 graphene Inorganic materials 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 239000004642 Polyimide Substances 0.000 claims description 5
- 229960000583 acetic acid Drugs 0.000 claims description 5
- 239000002390 adhesive tape Substances 0.000 claims description 5
- 238000005804 alkylation reaction Methods 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 5
- 239000000920 calcium hydroxide Substances 0.000 claims description 5
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000010908 decantation Methods 0.000 claims description 5
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 5
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 5
- 238000004108 freeze drying Methods 0.000 claims description 5
- 239000012362 glacial acetic acid Substances 0.000 claims description 5
- 230000005291 magnetic effect Effects 0.000 claims description 5
- 238000003760 magnetic stirring Methods 0.000 claims description 5
- 229920001721 polyimide Polymers 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
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- 238000010992 reflux Methods 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 239000002893 slag Substances 0.000 claims description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- 239000012265 solid product Substances 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000391 magnesium silicate Substances 0.000 claims description 4
- 229910052919 magnesium silicate Inorganic materials 0.000 claims description 4
- 235000019792 magnesium silicate Nutrition 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 229920002401 polyacrylamide Polymers 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
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- 229920002873 Polyethylenimine Polymers 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 15
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- MKPXGEVFQSIKGE-UHFFFAOYSA-N [Mg].[Si] Chemical compound [Mg].[Si] MKPXGEVFQSIKGE-UHFFFAOYSA-N 0.000 abstract 1
- 239000002920 hazardous waste Substances 0.000 abstract 1
- 229920000620 organic polymer Polymers 0.000 abstract 1
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- 239000002245 particle Substances 0.000 description 9
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- OFOBLEOULBTSOW-UHFFFAOYSA-L Malonate Chemical compound [O-]C(=O)CC([O-])=O OFOBLEOULBTSOW-UHFFFAOYSA-L 0.000 description 6
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- 102000004190 Enzymes Human genes 0.000 description 3
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Classifications
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
- A62D3/33—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by chemical fixing the harmful substance, e.g. by chelation or complexation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07K—PEPTIDES
- C07K14/00—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof
- C07K14/435—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans
- C07K14/78—Connective tissue peptides, e.g. collagen, elastin, laminin, fibronectin, vitronectin or cold insoluble globulin [CIG]
-
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Abstract
The invention belongs to the field of solid hazardous waste treatment and resource utilization, and particularly discloses a preparation and application method of a chromium-removing ammonia-reducing agent of a chromium-containing collagen solution extracted from waste leather scraps, wherein the chromium-removing ammonia-reducing agent comprises a chromium ion replacement material, an electrostatic adsorption material, an ammonia-reducing material, a magnetic material and a coating material, and the chromium ion replacement material is prepared by grafting silicon dioxide with a silane coupling agent, malonic acid and citric acid; the electrostatic adsorption material is obtained by modifying an inorganic silicon-magnesium material; the ammonia-reducing material is obtained by synthesizing zeolite and modifying the zeolite; the magnetic material passes through Fe 2+ 、Fe 3+ Is prepared by synthesizing raw materials; the coating material is an organic polymer material; the coating material coats the chromium ion replacement material, the electrostatic adsorption material, the ammonia-reducing material and the magnetic material together through a process to obtain the chromium-removing ammonia-reducing agent. The invention is thatHas the advantages of simple process, low cost, thorough chromium removal, obvious ammonia reduction, suitability for industrial application and the like.
Description
Technical Field
The invention belongs to the field of solid dangerous waste treatment and resource utilization, and particularly relates to a preparation method and an application method of a chromium-removing ammonia-reducing agent of a chromium-containing collagen solution extracted from waste leather scraps.
Background
In the leather industry, chrome tanning has been the main tanning method for leather to date due to its excellent combination of properties. It is counted that 40% -45% of solid waste is produced per 1 ton of raw hide, and about 100 ten thousand tons of chromium-containing waste hide scraps are produced annually in China. Such waste is nationally classified as dangerous waste due to the heavy metal chromium content, which severely pollutes the environment and also hinders the sustainable development of the leather industry.
The waste chrome leather scraps contain more than 85 percent of collagen, and the collagen is an important resource, so that the recycling of the collagen in the waste chrome leather scraps has important social and economic significance. The leather scraps contain 2 to 4 percent of chromium element, and the application of the chromium removing agent of the chromium-containing collagen solution in the chromium-containing collagen solution is chelated with carboxyl, hydroxyl and amino in the collagen in leather, so how to remove Cr (III) from the leather scraps and maintain the higher recovery rate of the collagen becomes a research hot spot of a scientific worker, and the following schemes are summarized up to now: alkali method, acid method, oxidation method, enzyme method, and mixing method.
The principle of the alkali chromium removal is free OH - Enters the inner boundary of the chromium complex to replace collagen chelation to form Cr (OH) 3 The precipitate is then removed by press filtration with a plate filter press, which can remove most of the chromium, but a small amount of chromium remains in the collagen solution, and the chromium content is 10-100 mg/L. Zhao Jiahua (dechromization of waste leather scraps and investigation by composite alkaline method [ J ]]The chromium content of the collagen solution extracted by leather science and engineering, vol.26, no.5 Oct.2016:68-70) is 25-90ppm, and the chromium content of the industrial protein powder obtained by drying is 100-200 mg/Kg, which is higher than the national standard and is less than or equal to 50mg/Kg, so that the requirements of the actual market cannot be met.
The principle of acid chromium removal is as follows: COO under acidic conditions - Changing into COOH promotes the dissociation of chelate formed by chromium and collagen, and simultaneously, the acid radical ion and chromium carry out complexation reaction, thereby achieving the purpose of chromium removal. The acid method has the advantages of high collagen extraction rate, and has the defects of high collagen molecular decomposition degree, small molecular weight of the obtained product, incomplete chromium separation, wang Xian, and the like (study of phosphoric acid dechromization of blue wet leather [ J ]]Western leather, vo1.31No.19 Oct.2009:20-24) by acid process to obtain collagen solution with chromium content of hundreds ppm. Tryptophan, serine, tyrosine and the like in the hydrolysate are destroyed, and in industrial mass production, the acid treatment method is limited by equipment and is difficult to realize the process.
The principle of chromium removal by an oxidation method is as follows: trivalent chromium in the chrome-containing leather scraps is converted into hexavalent chromium through an oxidant, so that the tanning property of the chrome-containing leather scraps is lost, and collagen and chromium are separated through rinsing and filtering, so that the aim of removing the chromium is fulfilled. Sun Dangong (study of the method for oxidative dechromization of chromium-containing waste leather scraps [ J ]. Leather science and engineering, vol.12, no. 3)
Jun.2002:31-36) adopts an oxidation chromium removal process, and the chromium removal rate is up to more than 90 percent. The oxidation method has the advantages of high chromium removal speed, small damage degree to the structure of the collagen, bright color, high molecular weight of the obtained collagen and the like; the disadvantage is that hexavalent chromium with high toxicity is produced in the production process, and further treatment is required, so that the cost and the process difficulty are increased.
The principle of enzymatic chromium removal is that under the action of alkaline protease, peptide bonds in collagen fibers containing chrome leather scraps are hydrolyzed and dissolved in water, and chromium and OH are dissolved in the water - Combined to generate Cr (OH) 3 And (5) precipitation. The enzymatic method has the advantages of strong specificity, short reaction time, mild conditions, no corrosion to equipment and less damage to protein, and is a valuable technical route for efficiently and cleanly recovering the collagen. Zhou Wen et al (Preparation of High Molecular Weight Products by Crosslinking Protein Isolated from the Enzymatic Processing of ChromiumContaining Collagenous Waste: I.extraction of Gelatin J ]Leather science and engineering, vol.15, no. 2Apr.2005:3-7) has been studied by enzymatic methods, which have the advantages of mild conditions, environmental protection, etc., but the chromium removal rate and the collagen extraction rate are low, and the theories of controlling the action sites of the collagen fiber molecules and the enzymolysis end points by the enzymes are still unclear, thus limiting the application of the enzymatic methods.
There are also various methods used in combination, such as acid-base method (Zhao Shengzong, etc., optimization of CaO dechromization in acid-base combination treatment of chrome leather scraps [ J ], leather science and engineering, 30 (1): 17-22 Feb.2020), alkaline enzyme method (Jiang Xihuai, etc., technological method of extracting collagen from waste chrome leather scraps [ J ]. Chinese leather, vol.40N0.1 Jan.2011), acid-base oxidation method, etc., but the chromium content of the extracted collagen solution is generally more than 20ppm, and at the same time, there are other limitations, or the cost is too high, or the operation process is complex, or the existing equipment cannot be industrialized, and it is difficult to really realize industrialization.
Among the above methods, the alkaline method has the advantages of simple process, thorough chromium removal, high protein extraction and wide application in industry, but the alkaline method also has more problems, such as small molecular weight of hydrolyzed protein, and the generation of a certain amount of ammonia gas, which can influence the quality of protein, reduce the freshness of protein powder, and how to reduce the ammonia content in the extracting solution and improve the freshness of the product becomes a problem to be solved urgently by enterprises.
The chromium removal technology needs to meet the industrial requirements: firstly, the chromium in the collagen solution can be deeply removed, secondly, the chromium removing and ammonia reducing agent can be rapidly separated from the solution, thirdly, the operation is convenient and fast, and the production of enterprises is facilitated.
Disclosure of Invention
The alkali method is more thorough in chromium removal, but a few chromium in the obtained collagen liquid is still chelated with carboxyl, hydroxyl, amino and the like in the collagen; minority Cr (OH) 3 Converting into colloid; and part of chromium and hydroxyl groups generate polyhydroxy chromium plasma, and the three chromium-containing substances cannot be removed by a common precipitation method. The invention aims to prepare a chromium removal ammonia reduction agent, remove three chromium-containing substances which are difficult to remove by a precipitation filtration method and exist in a collagen solution, and can realize solid-liquid rapid separation. The collagen solution obtained by alkaline hydrolysis contains a certain amount of ammonia, so that the freshness of the protein powder is reduced, the quality of the protein powder is affected, the ammonia in the solution can be removed, the freshness of the product is improved, and the quality of the protein powder is improved.
Aiming at the problem that a few chromium in the collagen liquid is still chelated with the collagen and is difficult to remove, the technical solution idea of the invention is as follows: according to the rule that the ligand with strong coordination ability can replace the ligand with weak coordination ability, searching for a stronger ligand to replace chromium from the coordination of collagen, and removing the chromium by precipitation.
For the presence of a small number of Cr (OH) in solution 3 Colloid, a few polyhydroxy chromium complex ions, the technical solution thinks: based on the characteristic of charge of colloid particles and polyhydroxy chromium complex ions, the adsorption agent with the opposite charges is adopted, and the basic physical principle of electrostatic adsorption is utilized for removal.
Aiming at the technical solution that a certain amount of ammonia exists in the collagen protein solution to influence the quality of the protein powder and reduce the quality of the protein powder, the following technical solution thinking is adopted: the pH value is firstly adjusted to convert the solution into neutral or weak acid, so that the solution is converted into ammonium ions, and then the ammonium ions are exchanged with ions in the inorganic material for removal.
In practical production, it is very important to improve the efficiency of solid-liquid separation. The sedimentation rate of inorganic particulates in solution is directly related to the particle size of the particulate: the larger the particles, the faster the sedimentation velocity, and the more favorable the solid-liquid separation. The technical solution is as follows: firstly, a coating material is used for coating a plurality of materials together, so that the particle size of particles is increased, and the solid-liquid separation efficiency is improved; and secondly, a magnetic material is added under the magnetic action, and the quick separation from the solution is realized through a magnet.
The inventive idea
(1) Cr according to practice 3+ The ligand strong and weak sequences are as follows: the oxalate radical is more than the citrate radical, the malonate radical, the succinate radical, the phthalate radical, the acetate radical and the collagen carboxylate radical. The chromium chelated by the collagen can be replaced based on the strong coordination capacity of the citrate; however, citrate has a certain steric hindrance with a larger molecular weight, influences the permeation effect of the citrate in leather scraps tissues and further influences the chromium removal effect of the citrate, and in order to make up the defects in the aspect, a part of malonate is added into the system, so that the malonate has the characteristics of small molecular weight, small steric hindrance and strong permeability in leather scraps tissues, and the malonate and the citrate cooperate to remove chromium, so that the chromium coordination replacement is more thorough.
(2) Aiming at the condition that citrate, malonate and chromium element coordinate to generate soluble complex ions which cannot be precipitated, the citrate and malonate are grafted on the surfaces of the citrate and malonate by a chemical method to prepare a chromium ion displacer, and chromium is removed by means of sedimentation of nano silicon dioxide in a solution.
(3) In the powder of kaolinite, montmorillonite, diatomite and magnesium silicate, the surface of the particles in the aqueous solution is charged due to the high valence state of silicon-aluminum ions, and the powder has electrostatic attraction, so colloid and polyhydroxy chromium complex ions can be adsorbed. Immersing the powder in dilute acid, stirring, immersing, washing to thin and reduce the original layered structure, exposing active sites of Al and Si on the surface, obviously improving electrostatic attraction, drying, and calcining to obtain the electrostatic adsorption material. EDTA grafted on the surface of the electrostatic adsorbent further enhances the removal of chromium ions.
(4) Aiming at the problem that the freshness of protein powder is affected by the existence of a certain amount of ammonia in the collagen solution, zeolite is synthesized and activated to obtain the ammonia removal material. The zeolite has a silicon (aluminum) oxygen tetrahedral crystal structure, the zeolite framework contains excessive negative charges, metal cations are needed for neutralizing the negative charges in order to keep electric neutrality, and the metal cations are unstable in the zeolite structure and are easily replaced by cations in the solution; the zeolite pore canal is 300-1000pm generally, the diameter of ammonium ion is 286pm, the zeolite can directly enter the pore canal, larger ion can not enter the zeolite pore canal, and the zeolite pore canal can be selectively replaced with ammonium ion to achieve the purpose of removing ammonia; the ammonia removal rate can be greatly improved by activating zeolite.
(5) Because the nano silicon dioxide particles are smaller and the surface hydroxyl groups are rich, the sedimentation is slower in the solution, the sedimentation time is longer, and the idea of solving the problem is that: the solid magnetic material can be quickly separated from the solution through the magnet; the magnetic material, the chromium ion replacement material, the electrostatic adsorption material and the ammonia removal material are coated by the coating material, so that on one hand, the solid-liquid rapid separation is realized through the magnet, and on the other hand, the particles become larger when the substances are coated together, thereby being beneficial to rapid sedimentation.
(6) The chromium-removing ammonia-reducing agent for preparing the chromium-containing collagen solution by the inventive thought is composed of a chromium ion replacement material, an electrostatic adsorption material, an ammonia-reducing material, a magnetic material and a coating material, wherein the weight ratio of the five materials is 100:95-105:1000-1200:90-110:50-60 in sequence.
The preparation method of the chromium ion replacement material comprises the following steps: 1) Nano SiO 2 Preparation of pellets: the preparation method comprises the steps of adopting a classical sol-gel method to prepare, mixing 25-30 mL of secondary distilled water, 65-85 mL of absolute ethyl alcohol and 15-20 mL of ammonia water, heating to constant temperature in an oil bath at 35-40 ℃, dropwise adding 0.8g of 99% ethyl orthosilicate under strong stirring, continuously and vigorously stirring for reaction for 30-40 min, hydrolyzing the ethyl orthosilicate under alkaline condition to obtain silica spheres serving as seeds, dropwise adding 6.2g of ethyl orthosilicate, continuously reacting for 2-3 h, and finally centrifuging and drying to obtain the nano SiO 2 A pellet;
2) Nano SiO 2 Preparation of APTES: 10g of nano SiO of step 1) are reacted with 2 Pellets are added into 80-100 mL of absolute ethyl alcohol, suspension is obtained through ultrasonic dispersion, 60-80 mL of absolute ethyl alcohol and 25-35 mL of deionized water are respectively taken and added into a two-mouth flask, micro glacial acetic acid is added to adjust pH=5-6, 2-4 mL of silane coupling agent KH-550 (Kang Jin new material technology Co., dongguan) is added into the flask drop by drop, fully stirred and hydrolyzed, and then nano SiO is added 2 The pellet suspension was added dropwise to the flask, and the ethoxy (-OCH) group in the silane coupling agent was added 2 CH 3 ) Reacts with water to generate silicon hydroxyl (-Si-OH), which reacts with nano SiO 2 The silicon hydroxyl groups on the pellets are dehydrated and condensed to achieve the aim of grafting modification, the reaction is carried out for 18 to 24 hours at room temperature, the reaction liquid is centrifuged and then is washed and centrifuged by absolute ethyl alcohol, absolute THF and acetone respectively, the solid is dispersed by deionized water, and the white solid product is obtained after freeze drying, namely the product nano SiO 2 -APTES；
3) Preparation of alpha-bromocitric acid: the carboxylic acid and halogen are reacted under the action of a catalytic amount of reagent to convert the carboxylic acid into acyl halide, the alpha-H of the acyl halide has higher activity and is easy to be converted into enol, the alpha-hydrogen is substituted by the halogen to generate alpha-halogenated acyl halide, and then the alpha-halogenated carboxylic acid is obtained through an exchange reaction with the carboxylic acid, namely the Helone Wu Erha-Zelins reaction. Adding 10g of citric acid, 80-100 mL of absolute ethyl alcohol and 0.1-0.4 g of catalyst bromosuccinimide into a bromination reaction kettle, heating to 65-75 ℃, dropwise adding 18-22 mL of bromine, preserving heat for 3-4 hours at 65-75 ℃ after the dropwise adding is finished, and distilling under reduced pressure to remove redundant bromine, hydrogen bromide and ethanol to obtain alpha-bromocitric acid;
4) Preparation of alpha-bromomalonic acid: adding 10g of malonic acid, 80-100 mL of absolute ethyl alcohol, 0.1-0.3 g of catalyst bromosuccinimide, heating to 65-75 ℃, dropwise adding 17-19 mL of bromine, preserving heat for 3-4 hours at 65-75 ℃ after the dropwise adding is finished, and removing redundant bromine, hydrogen bromide and ethanol through reduced pressure distillation to prepare alpha-bromomalonic acid;
5) The chromium ion replacement material is SiO 2 Preparation of APTES-PC/CA: 60-80 mL deionized water is added into a three-necked flask, and 4g of alpha-bromocitric acid in the step 3) and 2 are added3g of alpha-bromomalonic acid obtained in the step 4) is put into a three-necked bottle, 0.2 to 0.3g of potassium carbonate is added, and the mixture is heated to constant temperature in an oil bath of 30 to 40 ℃ and fully stirred for 10 to 20 minutes; slowly adding 20-30 g of nano SiO of the step 2) 2 APTES, refluxing under magnetic stirring for 2-3 hr, suction filtering, washing with water, drying, grafting on nano SiO 2 The amino on the surface and the alpha-bromomalonic acid and the alpha-bromocitric acid undergo Huffman alkylation reaction to obtain a chromium ion replacement material, namely SiO 2 -APTES-PC/CA。
The electrostatic adsorption material contains one of carrier kaolinite, montmorillonite, diatomite and magnesium silicate, and is prepared by a series of steps:
1) Carrying out carrier activation treatment; 40g of one of kaolinite, montmorillonite, diatomite and magnesium silicate is weighed, added into 400mL of 0.75-1.25 mol/L sodium hydroxide solution and dispersed for 20-30 min by ultrasonic, so that more Al is arranged on the surface of the carrier 3+ ，Si 4+ Exposing out the plasma, increasing the surface charge of the carrier, reacting for 5-6 hours at 60-80 ℃, filtering, washing to be neutral, and drying to obtain the activated carrier;
2) Adding 20g of the activating carrier in the step 1) into a three-neck flask containing 80-100 mL of toluene, performing ultrasonic dispersion for 15-20 min, slowly heating the mixed solution to 105-110 ℃ under the protection of nitrogen (60-80 mL/min), and adding 3-5 g of 3-aminopropyl trimethyl ethyl silane (APTES) to obtain ethoxy (-OCH) in a silane coupling agent 2 CH 3 ) Can react with water to be converted into silicon hydroxyl (-Si-OH), which has dehydration condensation with silicon hydroxyl on an activated carrier, and is continuously stirred for 12 to 15 hours, then filtered and washed, and is purified by absolute ethyl alcohol for 12 to 15 hours, so as to remove unreacted ATPES, and then is dried for 12 to 15 hours at 70 to 80 ℃ in vacuum, thus obtaining the material used for experiments, namely the activated carrier-APTES;
3) Under the protection of nitrogen, 50-60 mL of dichloromethane and 0.025-0.035 mol of EDTA are removed, 2-3 mL of thionyl chloride is dropwise added at constant pressure, EDTA reacts with thionyl chloride to prepare acyl chloride, 1g of activated carrier-APTES in the step 2) is rapidly added, the acyl chloride reacts with 3-aminopropyl triethoxysilane on the surface of the activated carrier to generate an amide compound, the amide compound reacts for 2-3 hours at room temperature, filtering is carried out, 8mL of dichloromethane, 8mL of acetone, 10mL of deionized water, 10mL of 0.15-0.25 mol/L sodium bicarbonate solution and 10mL of deionized water are used for washing, and drying is carried out at 50-60 ℃ to obtain the product of activated carrier-APTES-EDTA, namely the electrostatic adsorption material.
The preparation method of the ammonia-reducing material comprises the following steps: (1) 6.5 to 7.5g of KOH and 6.5g of Al 2 (SO 4 ) 3 ·18H 2 O, 3.5-4.0 g of 10nm granular graphene oxide (Guangzhou Emi graphene technology Co., ltd.) is sequentially added into a beaker containing 600-650 mL of deionized water under stirring, and stirred for 30-40 min to obtain solution A;
(2) Weighing 500-550 mL of absolute ethyl alcohol, slowly adding 183g of ethyl orthosilicate under strong stirring in a beaker, and continuously stirring for 30-40 min after the dripping is finished to obtain a solution B;
(3) Slowly adding the solution B into the solution A under the stirring state, and continuing stirring for 60-70 min after the solution B is added; transferring the mixture into a reaction kettle with a polytetrafluoroethylene lining, reacting for 40-50 h in a baking oven at 165-175 ℃, washing the product to be neutral by deionized water after the reaction is finished, and drying in the baking oven at 90-100 ℃; placing the dried product in a muffle furnace, and roasting for 20-25 hours at 540-580 ℃ to obtain zeolite; the zeolite product is placed in 500ml of NaCl solution with the concentration of 0.8 to 1.4moL/L, and reacts for 8 to 12 hours in a water bath constant temperature oscillating box with the temperature of 30 to 45 ℃, and is washed clean by deionized water and dried, thus obtaining the ammonia-reducing material.
The preparation method of the magnetic material comprises the following steps: (1) Adding 20-30 mL of deionized water into 70-80 mL of ethylene glycol, stirring, adding 32.0g of isobutylamine and 6.0-7.0 g of diethanolamine, and stirring for 5-10 min to obtain solution A;
(2) 3.0g FeCl 2 .4H 2 O is dissolved in 30-40 mL of deionized water, 60-70 mL of ethylene glycol is added, and the solution B is obtained by stirring while adding;
(3) Adding 20-30 mL deionized water into 70-80 mL glycol, and adding 5.0g FeCl 3 .6H 2 O, stirring for 5min to obtain a solution C;
(4) Equally dividing the solution A into two parts, mixing one part with the solution B and mixing the other part with the solution C; mixing and stirring the two mixed solutions for 20-30 min, pouring the mixed solutions into a polyimide lining, covering, sealing by using an adhesive tape, placing the lining into an oven at 90-100 ℃, keeping the temperature for 5-10 h, naturally cooling to room temperature, separating a black product by using a magnet, washing with 100-150 mL of ionized water, washing with 100-150 mL of absolute ethyl alcohol for 2-4 times, and placing the lining into the oven at 30-40 ℃ for drying for 6-12 h to obtain the magnetic material ferroferric oxide.
The coating material is one of hydroxymethyl cellulose, carboxymethyl cellulose, polyacrylamide, polyethyleneimine and polyacrylamide, and a large amount of hydroxyl contained in the molecule can be used for coating together with a chromium ion replacement material, an electrostatic adsorption material, an ammonia-reducing material and a magnetic material through hydrogen bond and Van der Waals force action to obtain the chromium-removing ammonia-reducing agent, wherein the weight ratio of the five materials is 100:95-105:1000-1200:90-110:10-15 in sequence. The specific coating process comprises the following steps: 100g of chromium ion replacement material, 95-105 g of electrostatic adsorption material, 1000-1200 g of ammonia reduction material and 95-105 g of magnetic material are poured into a three-necked bottle and stirred for 30-40 min at normal temperature; spraying 2000-2400 mL of water solution with 50-60 g of coating material dissolved into a three-necked flask while stirring, then putting the product obtained by the above operation into a blast drier for drying, firstly drying at 70-80 ℃ for 1h, then heating to 110-115 ℃ for 1-1.5 h, and drying to obtain the chromium and ammonia removal agent.
In the invention, the combination of the chromium ion replacement material and the electrostatic adsorption material in the chromium-removing ammonia-reducing agent is a key for realizing deep chromium removal of the chromium-containing collagen.
In the invention, the use of the ammonia-reducing material is a key material for reducing the ammonia content and improving the freshness of the protein powder.
In the invention, one of the key factors for realizing the solid-liquid quick separation is realized by using the magnetic material, and the other four materials are coated together by the coating material, so that the method is also the key factor for realizing the solid-liquid quick separation.
The invention relates to an application of chromium-removing ammonia-reducing agent of a chromium-containing collagen solution, which comprises the following components in the collagen solution: the chromium content is 20.6mg/L, the collagen content is 203g/L, the pH is 9, and the ammonia content is 200mg/L. The specific chromium and ammonia removal operation steps are as follows: taking 1L of the solution, regulating the pH value to 10.5-11.5 by alkali, adding 12-18 g of chromium and ammonia removing agent, stirring and reacting for 2-3 h at 60-90 ℃ by controlling the pH value, adding sulfuric acid to regulate the pH value of the solution to 6-7, converting ammonia into ammonium ions, carrying out ion exchange and ammonia removal on the ammonium ions and ammonia reducing materials, continuing stirring for 2.5-3.5 h, stopping treatment and standing, adding a magnet under a three-necked bottle, realizing solid-liquid quick separation by utilizing magnetic effect and natural sedimentation effect, and obtaining the collagen solution and chromium slag by a decantation method.
The pH of the collagen solution is regulated to be 10.5-11.5 and maintained, alkali used in the process of regulating the pH is one or more of sodium hydroxide, potassium carbonate, sodium carbonate, calcium oxide, magnesium oxide and calcium hydroxide, and the reinforcing auxiliary means is that the reaction temperature is 60-90 ℃ and the strong stirring rotating speed is 100-300 r/min.
The raw materials are commercially available products well known to those skilled in the art unless otherwise specified in the present invention.
Compared with the prior art, the invention has the following advantages and effects:
the collagen solution obtained by alkaline hydrolysis of chrome-containing leather scraps contains three chrome-containing substances: a few chromium remains sequestered with carboxyl, hydroxyl, amino, etc. groups in collagen; minority Cr (OH) 3 A colloid; part of chromium and hydroxyl form polyhydroxy chromium complex ions, and the conventional chromium removing agent cannot remove the substances; the collagen solution obtained by the alkaline method contains a certain amount of ammonia, the ammonia content is directly related to the freshness of the product, the quality of the protein powder is affected, and how to reduce the ammonia content in the collagen is not reported at present. The chromium-removing ammonia-reducing agent of the chromium-containing collagen solution comprises the following components:
firstly, the strong coordination capability of citrate and chromium ions is utilized, and the molecular weight and permeability of malonic acid are small, so that the chromium ions in the collagen are replaced under the coordination of the citrate and the chromium ions.
Second is nano SiO 2 The pellets, citric acid and malonic acid are grafted to prepare the chromium ion replacement material, namely SiO 2 APTES-PC/CA, the material is solidThe displaced chromium ions are now removed by precipitation.
Thirdly, the electrostatic adsorption material carrier is activated by alkali to lead the surface to have more positive charges, which is beneficial to Cr (OH) 3 The colloid and polyhydroxy chromium complex ions are adsorbed.
Fourthly, EDTA is grafted on the surface of the electrostatic adsorption material, on one hand, strong coordination of EDTA and chromium ions is utilized to remove chromium, and on the other hand, the adsorption of the EDTA and chromium-containing collagen is facilitated.
Fifthly, the ammonia-reducing material reduces ammonium ions in an ion exchange mode and improves the freshness of products.
And sixthly, adding a magnetic material, and utilizing a magnet to realize solid-liquid rapid separation.
And seventhly, adding a coating material to coat the chromium ion replacement material, the electrostatic adsorption material, the ammonia-reducing material and the magnetic material together, so that solid particles become larger, and the chromium-removing ammonia-reducing agent is beneficial to quickly settling to realize solid-liquid efficient separation.
Drawings
FIG. 1 is a schematic structural diagram of a chromium and ammonia removal agent material prepared by the invention.
Detailed Description
The invention is further illustrated by the following examples.
Example 1
The preparation method of the chromium ion replacement material comprises the following steps:
1) Nano SiO 2 Preparation of pellets: mixing 27mL of deionized water, 75mL of absolute ethyl alcohol and 18mL of ammonia water, heating to constant temperature in an oil bath at 35 ℃, dropwise adding 0.8g of 99% ethyl orthosilicate with strong stirring, continuously and vigorously stirring for reaction for 35min to obtain a silica sphere seed solution, then dropwise adding 6.2g of ethyl orthosilicate, continuously reacting for 2.5h, and finally centrifuging and drying to obtain nano SiO 2 A pellet;
2) Nano SiO 2 Preparation of APTES: 10g of nano SiO of step 1) are reacted with 2 Pellets are dispersed in 90mL absolute ethyl alcohol and evenly dispersed by ultrasonic, thus obtaining nano SiO 2 70mL of absolute ethyl alcohol and 30mL of deionized water are respectively taken as the pellet suspension, added into a two-mouth flask, and micro glacial acetic acid is added to adjust the pH value to be between 5 and 6,dropwise adding 3mL of silane coupling agent KH-550 into the flask, fully stirring for hydrolysis, and then adding nano SiO 2 Dropwise adding the pellet suspension into a flask, reacting at room temperature for 21h, centrifuging the reaction solution, washing and centrifuging the reaction solution respectively by 25mL of absolute ethyl alcohol, 15mL of absolute tetrahydrofuran and 15mL of acetone, dispersing the solid by 30mL of deionized water, and freeze-drying to obtain a white solid product, namely nano SiO 2 -APTES；
3) Preparation of alpha-bromocitric acid: adding 10g of citric acid, 90mL of absolute ethyl alcohol and 0.25g of bromosuccinimide catalyst into a bromination reaction kettle, heating to 70 ℃, dropwise adding 20mL of bromine, after the dropwise adding is finished, preserving the temperature for 3.5h at 70 ℃, and distilling under reduced pressure to remove redundant bromine, hydrogen bromide and ethanol to obtain alpha-bromocitric acid;
4) Preparation of alpha-bromomalonic acid: adding 10mL of malonic acid, 90mL of absolute ethyl alcohol, adding 0.2g of bromosuccinimide serving as a catalyst, heating to 70 ℃, dropwise adding 18mL of bromine, preserving the temperature at 70 ℃ for 3.5h after the dropwise adding is finished, and distilling under reduced pressure to remove redundant bromine, hydrogen bromide and ethanol to obtain alpha-bromomalonic acid;
5) Chromium ion replacement material, namely SiO 2 Preparation of APTS-PC/CA: 70mL of deionized water is added into a three-necked flask, 4g of alpha-bromocitric acid in the step 3) and 2.5g of alpha-bromomalonic acid in the step 4) are put into the three-necked flask, 0.25g of potassium carbonate is added, and the mixture is heated to constant temperature in an oil bath at 30-40 ℃ and fully stirred for 15min; then 25g of nano SiO of step 2) is slowly added 2 APTES, refluxing for 2.5h under magnetic stirring, suction filtering, washing with water, drying, grafting on nano SiO 2 The amino on the surface and the alpha-bromomalonic acid and the alpha-bromocitric acid undergo Huffman alkylation reaction to obtain a chromium ion replacement material, namely SiO 2 -APTES-PC/CA。
The electrostatic adsorption material contains carrier diatomite, and is obtained by selecting the diatomite carriers through modification;
1) Carrying out carrier activation treatment; 40g of diatomite is weighed, 400mL of 1mOl/L hydrochloric acid solution is added for ultrasonic dispersion for 25min, and the mixture reacts for 5.5h at 70 ℃, is filtered, washed to be neutral and dried to obtain an activated carrier;
2) Adding 20g of the activation carrier in the step 1) into a three-neck flask containing 90mL of toluene, performing ultrasonic dispersion for 15min, slowly heating the mixed solution to 105 ℃ under the protection of 70mL/min of nitrogen flow, adding 4g of 3-aminopropyl triethoxysilane, continuously stirring for 13.5h, filtering, washing, purifying with absolute ethyl alcohol for 13.5h, and performing vacuum drying at 75 ℃ for 13.4h to obtain the activation carrier APTES;
3) Under the protection of nitrogen, 55mL of dichloromethane and 0.030moL of EDTA are removed, 2.5mL of thionyl chloride is dropwise added at constant pressure, 1g of APTES serving as the activating carrier in the step 2) is rapidly added, the reaction is carried out for 2.5h at room temperature, filtration is carried out, and the electrostatic adsorbing material is obtained by washing with 8mL of dichloromethane, 8mL of acetone, 10mL of deionized water, 10mL of 0.2moL/L aqueous sodium bicarbonate solution and 10mL of deionized water, and drying at 55 ℃.
The preparation method of the ammonia-reducing material comprises the following steps: (1) 7g KOH,6.5g Al 2 (SO 4 ) 3 ·18H 2 O,4.0g of 10nm granular graphene oxide is sequentially added into a beaker containing 650mL of deionized water under a stirring state, and stirring is carried out for 35min to obtain a solution A;
(2) Weighing 500mL of absolute ethyl alcohol in a beaker, slowly adding 183g of ethyl orthosilicate under strong stirring, and continuously stirring for 30min after the dripping is finished to obtain a solution B;
(3) Slowly adding the solution B into the solution A under the stirring state, and continuing stirring for 65min after the solution B is added; transferring to a reaction kettle with a polytetrafluoroethylene lining, reacting for 45h in a baking oven at 170 ℃, washing the product to be neutral by deionized water after the reaction is finished, and drying in the baking oven at 95 ℃; placing the dried product in a muffle furnace, and roasting at 560 ℃ for 22.5 hours to obtain zeolite; the zeolite product is placed in 500mL of 1mOl/L NaCl solution, reacted for 10h in a water bath constant temperature shaking box at 38 ℃, washed clean by deionized water and dried to obtain the ammonia-reducing material.
The preparation method of the magnetic material comprises the following steps: (1) Adding 25mL of deionized water into 75mL of ethylene glycol, stirring, adding 32.0g of isobutylamine and 6.5g of diethanolamine, and stirring for 8min to obtain solution A;
(2) 3.0g FeCl 2 .4H 2 O was dissolved in 35mL deionized water and 65mL ethylene glycol was added whileAdding and stirring to obtain a solution B;
(3) 25mL of deionized water was added to 75mL of ethylene glycol followed by 5.0g of FeCl 3 .6H 2 O, stirring for 5min to obtain a solution C;
(4) Equally dividing the solution A into two parts, mixing one part with the solution B and mixing the other part with the solution C; mixing and stirring the two mixed solutions for 25min, pouring the mixed solution into a polyimide lining, covering, sealing by using an adhesive tape, placing the lining into an oven at 95 ℃, keeping the temperature for 7.5h, naturally cooling to the room temperature, separating a black product by using a magnet, washing with 125mL of ionized water, washing with 125mL of absolute ethyl alcohol for 3 times, and placing the lining into the oven at 30 ℃ for drying for 9h to obtain the magnetic material ferroferric oxide.
100g of chromium ion replacement material, 100g of electrostatic adsorption material, 1100g of ammonia reduction material and 100g of magnetic material are poured into a three-necked bottle, and stirred at normal temperature for 35min; spraying 2200mL of water to dissolve 55g of polyacrylamide into a three-necked bottle while stirring, then putting the product obtained by the above operation into a blast drier for drying, firstly drying at 75 ℃ for 1h, then heating to 110 ℃ for 1h, and drying to obtain the chromium and ammonia removal agent.
Taking chromium-containing waste blue leather scraps (Cr) of cow leather of leather technology and technology Co., ltd 2 O 3 3.5 percent of collagen is 80 percent, ash content is 5.5 percent) dry weight is 6.5Kg, 15L of water and 650g of calcium oxide are added, stirring reaction is carried out for 4 hours at 100 ℃, 4.5Kg of filter residue is obtained by filtering, 14L of filtrate, the chromium content in the filtrate is 20.6mg/L, the collagen content is 203g/L, the pH value is 9.0, the ammonia content is 200mg/L, and the chromium removal in the process reaches 99.8 percent. Taking 1L of the filtrate, adjusting the pH to 10.5 by potassium hydroxide (maintaining the pH of the system to 10.5 in the treatment process), and then adding 16.0g of the prepared chromium and ammonia removal agent into the solution at the temperature of 60 ℃; stirring for 2h; adding sulfuric acid to adjust the pH value of the solution to 6, continuously stirring for 2.5 hours, stopping the treatment and standing, adding a magnet under a three-necked bottle, utilizing the magnetic effect and natural sedimentation, quickly separating solid from liquid, obtaining collagen solution and chromium slag by a decantation method, and finally carrying out solid-liquid separation.
Example two
The preparation method of the chromium ion replacement material comprises the following steps:
1) Nano SiO 2 Preparation of pellets:mixing 25mL of deionized water, 65mL of absolute ethyl alcohol and 15mL of ammonia water, heating to constant temperature in an oil bath at 35 ℃, dropwise adding 0.8g of 99% ethyl orthosilicate with strong stirring, continuously and vigorously stirring for reaction for 30min to obtain a silica sphere seed solution, then dropwise adding 6.2g of ethyl orthosilicate, continuously reacting for 2h, and finally centrifuging and drying to obtain nano SiO 2 A pellet;
2) Nano SiO 2 Preparation of APTES: 10g of nano SiO of step 1) are reacted with 2 Pellets are dispersed in 80mL absolute ethyl alcohol and evenly dispersed by ultrasonic, thus obtaining nano SiO 2 Adding 60mL of absolute ethyl alcohol and 25mL of deionized water into a two-necked flask respectively, adding a trace amount of glacial acetic acid to adjust the pH value to be between 5 and 6, dropwise adding 2mL of silane coupling agent KH-550 into the flask, fully stirring and hydrolyzing, and then adding nano SiO 2 Dropwise adding the pellet suspension into a flask, reacting at room temperature for 18h, centrifuging the reaction solution, washing and centrifuging the reaction solution respectively by 25mL of absolute ethyl alcohol, 15mL of absolute tetrahydrofuran and 15mL of acetone, dispersing the solid by 30mL of deionized water, and freeze-drying to obtain a white solid product, namely nano SiO 2 -APTES；
3) Preparation of alpha-bromocitric acid: adding 10g of citric acid, 80mL of absolute ethyl alcohol and 0.1g of bromosuccinimide catalyst into a bromination reaction kettle, heating to 65 ℃, dropwise adding 18mL of bromine, after the dropwise adding is finished, preserving the temperature for 3 hours at 65 ℃, and distilling under reduced pressure to remove redundant bromine, hydrogen bromide and ethanol to obtain alpha-bromocitric acid;
4) Preparation of alpha-bromomalonic acid: adding 10mL of malonic acid, 80mL of absolute ethyl alcohol, adding 0.1g of bromosuccinimide serving as a catalyst, heating to 65 ℃, dropwise adding 17mL of bromine, preserving heat for 3 hours at 65 ℃ after the dropwise adding is finished, and distilling under reduced pressure to remove redundant bromine, hydrogen bromide and ethanol to obtain alpha-bromomalonic acid;
5) Chromium ion replacement material, namely SiO 2 Preparation of APTS-PC/CA: 60mL of deionized water is added into a three-necked flask, 4g of alpha-bromocitric acid in the step 3) and 2g of alpha-bromomalonic acid in the step 4) are put into the three-necked flask, 0.2g of potassium carbonate is added, and the mixture is heated to constant temperature in an oil bath at 30 ℃ and fully stirred for 10min; slowly adding 20g of nano SiO of the step 2) 2 APTES, refluxing under magnetic stirring for 2 hr, suction filtering, washing with water, drying, and grafting on nano SiO 2 The amino on the surface and the alpha-bromomalonic acid and the alpha-bromocitric acid undergo Huffman alkylation reaction to obtain a chromium ion replacement material, namely SiO 2 -APTES-PC/CA。
The electrostatic adsorption material contains carrier kaolinite, and is obtained by modifying the carrier kaolinite;
1) Carrying out carrier activation treatment; weighing 40g of kaolinite, adding 400mL of 0.75mol/L hydrochloric acid solution, performing ultrasonic dispersion for 20min, reacting at 60 ℃ for 5h, filtering, washing to be neutral, and drying to obtain an activated carrier;
2) Adding 20g of the activation carrier in the step 1) into a three-neck flask containing 80mL of toluene, performing ultrasonic dispersion for 15min, slowly heating the mixed solution to 105 ℃ under the protection of a nitrogen flow of 60mL/min, adding 3g of 3-aminopropyl triethoxysilane, continuously stirring for 12h, filtering, washing, purifying with absolute ethyl alcohol for 12h, and performing vacuum drying at 70 ℃ for 12h to obtain the activation carrier-APTES;
3) 50mL of dichloromethane and 0.025moL of EDTA are removed under the protection of nitrogen, 2mL of thionyl chloride is added dropwise at constant pressure, 1g of the active carrier APTES in the step 2) is added rapidly, the reaction is carried out for 2 hours at room temperature, filtration is carried out, the mixture is washed by 8mL of dichloromethane, 8mL of acetone, 10mL of deionized water, 10mL of 0.15moL/L sodium bicarbonate aqueous solution and 10mL of deionized water, and the mixture is dried at 50 ℃ to obtain the electrostatic adsorption material.
The preparation method of the ammonia-reducing material comprises the following steps: (1) 6.5g KOH,6.5g Al 2 (SO 4 ) 3 ·18H 2 O,3.5g of 10nm granular graphene oxide is sequentially added into a beaker containing 600mL of deionized water under a stirring state, and the mixture is stirred for 30min to obtain a solution A;
(2) Weighing 500mL of absolute ethyl alcohol in a beaker, slowly adding 183g of ethyl orthosilicate under strong stirring, and continuously stirring for 30min after the dripping is finished to obtain a solution B;
(3) Slowly adding the solution B into the solution A under the stirring state, and continuing stirring for 60min after the solution B is added; transferring to a reaction kettle with a polytetrafluoroethylene lining, reacting for 40 hours in a baking oven at 165 ℃, washing the product to be neutral by deionized water after the reaction is finished, and drying in the baking oven at 90 ℃; placing the dried product in a muffle furnace, and roasting for 20 hours at 540 ℃ to obtain zeolite; the zeolite product is placed in 500mL of 0.8mol/L NaCl solution, reacted for 8 hours in a water bath constant temperature shaking box at 30 ℃, washed clean by deionized water and dried to obtain the ammonia-reducing material.
The preparation method of the magnetic material comprises the following steps: (1) Adding 20mL of deionized water into 70mL of ethylene glycol, stirring, adding 32.0g of isobutylamine and 6.0g of diethanolamine, and stirring for 5min to obtain solution A;
(2) 3.0g FeCl 2 .4H 2 O is dissolved in 30mL of deionized water, 60mL of ethylene glycol is added, and the solution B is obtained by stirring while adding;
(3) 20mL of deionized water was added to 70mL of ethylene glycol followed by 5.0g of FeCl 3 .6H 2 O, stirring for 5min to obtain a solution C;
(4) Equally dividing the solution A into two parts, mixing one part with the solution B and mixing the other part with the solution C; mixing and stirring the two mixed solutions for 20min, pouring the mixed solution into a polyimide lining, covering, sealing by using an adhesive tape, putting the lining into an oven at 90 ℃, keeping the temperature constant for 5h, naturally cooling to the room temperature, separating a black product by using a magnet, washing with 100mL of ionized water, washing with 100mL of absolute ethyl alcohol for 2 times, and drying in the oven at 30 ℃ for 6h to obtain the magnetic material ferroferric oxide.
100g of chromium ion replacement material, 95g of electrostatic adsorption material, 1000g of ammonia reduction material and 95g of magnetic material are poured into a three-necked bottle, and stirred for 30min at normal temperature; spraying 2000mL of water to dissolve 50g of hydroxymethyl cellulose into a three-necked bottle while stirring, then putting the product obtained by the above operation into a blast drier for drying, firstly drying at 70 ℃ for 1h, then heating to 110 ℃ for 1-1.5 h, and drying to obtain the chromium and ammonia removal agent.
Taking chromium-containing waste blue leather scraps (Cr) of cow leather of leather technology and technology Co., ltd 2 O 3 3.5 percent of collagen with 80 percent and 5.5 percent of ash content by dry weight of 6.5Kg, 15L of water and 650g of calcium oxide are added, stirred and reacted for 4 hours at 100 ℃, and filtered to obtain 4.5Kg of filter residue, 14L of filtrate, wherein the chromium content in the filtrate is 20.6mg/L, the collagen content is 203g/L, the pH value is 9.0, and the ammonia content is 200mg/LThe chromium removal in the process reaches 99.8 percent. Taking 1L of the filtrate, adjusting the pH to 10.5 by using calcium hydroxide (the pH of a system is maintained to be 10.5 in the treatment process), and then adding 12.0g of the prepared chromium and ammonia removal agent into the solution at the temperature of 60 ℃; stirring for 2h; adding sulfuric acid to adjust the pH value of the solution to 6, continuously stirring for 2.5 hours, stopping the treatment and standing, adding a magnet under a three-necked bottle, utilizing the magnetic effect and natural sedimentation, quickly separating solid from liquid, obtaining collagen solution and chromium slag by a decantation method, and finally carrying out solid-liquid separation.
Example III
The preparation method of the chromium ion replacement material comprises the following steps:
1) Nano SiO 2 Preparation of pellets: mixing 30mL of deionized water, 85mL of absolute ethyl alcohol and 20mL of ammonia water, heating to constant temperature in an oil bath at 40 ℃, dropwise adding 0.8g of 99% ethyl orthosilicate with strong stirring, continuously and vigorously stirring for reaction for 40min to obtain a silica sphere seed solution, then dropwise adding 6.2g of ethyl orthosilicate, continuously reacting for 3h, and finally centrifuging and drying to obtain nano SiO 2 A pellet;
2) Nano SiO 2 Preparation of APTES: 10g of nano SiO of step 1) are reacted with 2 Pellets are dispersed in 100mL absolute ethyl alcohol and evenly dispersed by ultrasonic, thus obtaining nano SiO 2 Adding 80mL of absolute ethyl alcohol and 35mL of deionized water into a two-necked flask respectively, adding a trace amount of glacial acetic acid to adjust the pH value to be between 5 and 6, dropwise adding 4mL of silane coupling agent KH-550 into the flask, fully stirring and hydrolyzing, and then adding nano SiO 2 Dropwise adding the pellet suspension into a flask, reacting at room temperature for 24 hours, centrifuging the reaction solution, washing and centrifuging the reaction solution respectively by 25mL of absolute ethyl alcohol, 15mL of absolute tetrahydrofuran and 15mL of acetone, dispersing the solid by 30mL of deionized water, and freeze-drying to obtain a white solid product, namely the nano SiO 2 -APTES；
3) Preparation of alpha-bromocitric acid: adding 10g of citric acid, 100mL of absolute ethyl alcohol and 0.4g of bromosuccinimide catalyst into a bromination reaction kettle, heating to 75 ℃, dropwise adding 22mL of bromine, after the dropwise adding is finished, preserving the temperature for 4 hours at 75 ℃, and distilling under reduced pressure to remove redundant bromine, hydrogen bromide and ethanol to obtain alpha-bromocitric acid;
4) Preparation of alpha-bromomalonic acid: adding 10mL of malonic acid, 100mL of absolute ethyl alcohol, adding 0.3g of bromosuccinimide serving as a catalyst, heating to 75 ℃, dropwise adding 19mL of bromine, preserving the temperature at 75 ℃ for 4 hours after the dropwise adding is finished, and distilling under reduced pressure to remove redundant bromine, hydrogen bromide and ethanol to obtain alpha-bromomalonic acid;
5) Chromium ion replacement material, namely SiO 2 Preparation of APTS-PC/CA: 80mL of deionized water is added into a three-necked flask, 4g of alpha-bromocitric acid in the step 3) and 3g of alpha-bromomalonic acid in the step 4) are put into the three-necked flask, 0.3g of potassium carbonate is added, and the mixture is heated to constant temperature in an oil bath at 40 ℃ and fully stirred for 20min; slowly adding 30g of nano SiO of the step 2) 2 APTES, refluxing under magnetic stirring for 3 hr, suction filtering, washing with water, drying, and grafting on nano SiO 2 The amino on the surface and the alpha-bromomalonic acid and the alpha-bromocitric acid undergo Huffman alkylation reaction to obtain a chromium ion replacement material, namely SiO 2 -APTES-PC/CA。
The electrostatic adsorption material contains carrier montmorillonite, and is obtained by selecting montmorillonite for modification;
1) Carrying out carrier activation treatment; weighing 40g of montmorillonite, adding 400mL of 1.25mol/L hydrochloric acid solution, performing ultrasonic dispersion for 30min, reacting at 80 ℃ for 6h, filtering, washing to be neutral, and drying to obtain an activated carrier;
2) Adding 20g of the activation carrier in the step 1) into a three-neck flask containing 100mL of toluene, performing ultrasonic dispersion for 20min, slowly heating the mixed solution to 110 ℃ under the protection of 80mL/min of nitrogen flow, adding 5g of 3-aminopropyl triethoxysilane, continuously stirring for 15h, filtering, washing, purifying with absolute ethyl alcohol for 15h, and performing vacuum drying at 80 ℃ for 15h to obtain the activation carrier-APTES;
3) 60mL of dichloromethane and 0.035moL of EDTA are removed under the protection of nitrogen, 3mL of thionyl chloride is added dropwise at constant pressure, 1g of APTES serving as the activating carrier in the step 2) is added rapidly, the reaction is carried out for 3 hours at room temperature, filtration is carried out, and the electrostatic adsorbing material is obtained by washing with 8mL of dichloromethane, 8mL of acetone, 10mL of deionized water, 10mL of 0.25moL/L sodium bicarbonate aqueous solution and 10mL of deionized water, and drying at 60 ℃.
Of ammonia-lowering materialsThe preparation method comprises the following steps: (1) 7.5g KOH,6.5g Al 2 (SO 4 ) 3 ·18H 2 O,4.0g of 10nm granular graphene oxide is sequentially added into a beaker containing 650mL of deionized water in a stirring state, and stirring is carried out for 40min to obtain a solution A;
(2) Weighing 550mL of absolute ethyl alcohol in a beaker, slowly adding 183g of ethyl orthosilicate under strong stirring, and continuously stirring for 40min after the dripping is finished to obtain a solution B;
(3) Slowly adding the solution B into the solution A under the stirring state, and continuing stirring for 70min after the solution B is added; transferring to a reaction kettle with a polytetrafluoroethylene lining, reacting for 50 hours in a baking oven at 175 ℃, washing the product to be neutral by deionized water after the reaction is finished, and drying in the baking oven at 100 ℃; placing the dried product in a muffle furnace, and roasting for 25 hours at 580 ℃ to obtain zeolite; the zeolite product is placed in 500mL of 1.4mol/L NaCl solution, reacted for 12 hours in a water bath constant temperature shaking box at 45 ℃, washed clean by deionized water and dried to obtain the ammonia-reducing material.
The preparation method of the magnetic material comprises the following steps: (1) Adding 30mL of deionized water into 80mL of ethylene glycol, stirring, adding 32.0g of isobutylamine and 7.0g of diethanolamine, and stirring for 10min to obtain solution A;
(2) 3.0g FeCl 2 .4H 2 O is dissolved in 40mL of deionized water, 70mL of ethylene glycol is added, and the solution B is obtained by stirring while adding;
(3) 30mL of deionized water was added to 80mL of ethylene glycol followed by 5.0g of FeCl 3 .6H 2 O, stirring for 5min to obtain a solution C;
(4) Equally dividing the solution A into two parts, mixing one part with the solution B and mixing the other part with the solution C; mixing and stirring the two mixed solutions for 30min, pouring the mixed solution into a polyimide lining, covering, sealing by using an adhesive tape, putting the lining into an oven at 100 ℃, keeping the temperature constant for 10h, naturally cooling to the room temperature, separating a black product by using a magnet, washing with 150mL of ionized water, washing with 150mL of absolute ethyl alcohol for 4 times, and drying in the oven at 40 ℃ for 12h to obtain the magnetic material ferroferric oxide.
100g of chromium ion replacement material, 105g of electrostatic adsorption material, 1200g of ammonia reduction material and 105g of magnetic material are poured into a three-necked bottle, and stirred for 40min at normal temperature; spraying 2400mL of water to dissolve 60g of carboxymethyl cellulose into a three-necked flask while stirring, then putting the product obtained by the above operation into a blast drier for drying, firstly drying at 80 ℃ for 1h, then heating to 115 ℃ for 1.5h, and drying to obtain the chromium and ammonia removal agent.
Taking chromium-containing waste blue leather scraps (Cr) of cow leather of leather technology and technology Co., ltd 2 O 3 3.5 percent of collagen is 80 percent, ash content is 5.5 percent) dry weight is 6.5Kg, 15L of water and 650g of calcium oxide are added, stirring reaction is carried out for 4 hours at 100 ℃, 4.5Kg of filter residue is obtained by filtering, 14L of filtrate, the chromium content in the filtrate is 20.6mg/L, the collagen content is 203g/L, the pH value is 9.0, the ammonia content is 200mg/L, and the chromium removal in the process reaches 99.8 percent. Taking 1L of the filtrate, adjusting the pH to 11.5 by using calcium hydroxide (the pH of a system is maintained to be 11.5 in the treatment process), and then adding 18.0g of the prepared chromium and ammonia removal agent into the solution at the temperature of 80 ℃; stirring for 3h; adding sulfuric acid to regulate pH value to 7, stirring for 3.5 hr, stopping treatment, standing, adding magnet under the three-necked flask, magnetically separating solid from liquid, and decanting to obtain collagen solution and chromium residue.
TABLE 1 chromium, ammonia content and separation time after use of three chromium removal and ammonia reduction agents
The above experiment results are shown in table 1, and the chromium removal effect of the second embodiment is best, the ammonia reduction and solid-liquid separation time of the second embodiment is almost the same as that of the third embodiment, so that the overall effect of the second embodiment is best, and the following comparative experiments are carried out with the second embodiment.
1) Comparative market products: the model of the chromium remover manufactured by Guangzhou city vast water treatment technology Co., ltd is TMT-30A, RY-15, and the comparative effect is shown in Table 2:
TABLE 2 comparison of chromium and ammonia content and separation time after use of the three products
2) Other comparative experiments
TABLE 3 chromium content and separation time after treatment of different materials
As can be seen from table 3, firstly, the chromium removal effect of adding citric acid or malonic acid is obviously increased, and meanwhile, the effect of adding citric acid or malonic acid is more obvious, and the citric acid or malonic acid and malonic acid play a role in coordination; secondly, the electrostatic adsorption material remarkably improves the chromium removal effect through activation treatment and grafting EATD; thirdly, the solid-liquid separation time of the coating material is greatly reduced; fourthly, the ammonia-reducing material can obviously reduce the ammonia content in the collagen; the activation treatment effect of the five-ammonia-reduction material is obvious compared with that of the untreated material; the six magnetic materials greatly shorten the solid-liquid separation time.
Product performance comparison
1. Taking chromium-containing waste blue leather scraps (Cr) of cow leather of leather technology and technology Co., ltd 2 O 3 6.5Kg dry weight of 3.5 percent of collagen with 80 percent and 5.5 percent of ash content is added with 15L of water and 650g of calcium oxide, stirred and reacted for 4 hours at 100 ℃, and filtered to obtain 4.5Kg filter residue and 14L of filtrate. The filtrate contains 20.6mg/L of chromium, 230g/L of collagen, 9.0 pH and 200mg/L of ammonia, 5L of filtrate is taken, sulfuric acid is added to adjust the pH value of the solution to 6.5, stirring is carried out for 3.0h, then the treatment is stopped, the rest is carried out, then the solid and the liquid are separated, the solution is concentrated, and the powder is sprayed by a miniature spray dryer to obtain 1kg of protein powder which is 'non-chromium-removed ammonia-reduced protein powder'
2) Taking chromium-containing waste blue leather scraps (Cr) of cow leather of leather technology and technology Co., ltd 2 O 3 6.5Kg dry weight of 3.5 percent of collagen with 80 percent and 5.5 percent of ash content is added with 15L of water and 650g of calcium oxide, stirred and reacted for 4 hours at 100 ℃, and filtered to obtain 4.5Kg filter residue and 14L of filtrate. The filtrate contains 20.6mg/L of chromium, 230g/L of collagen, pH 9.0 and 200mg/L of ammonia, 5L of the filtrate is taken, the pH is adjusted to 11.0 by calcium hydroxide (the pH of the system is maintained to 11.0 during the treatment), and then the solution is added15.0g of chromium-removing ammonia-reducing agent, and stirring for 2.5h at the temperature of 70 ℃; and adding sulfuric acid to adjust the pH value of the solution to 6.5, continuously stirring for 3.0h, stopping the treatment, standing, using a magnet and natural sedimentation, rapidly separating solid from liquid, and obtaining the collagen solution and the chromium slag by a decantation method. Concentrating the solution, and spraying powder by a miniature spray dryer to obtain 1kg of protein powder, wherein the protein powder is chromium-removing ammonia-reducing protein powder.
The results of the tests on the chromium content, ash content, quick solubility and bulk density of the four proteins of 'non-chromium protein powder', 'Funew Dacheng biotechnology Co., ltd', 'Shandong Huasheng chemical technology Co., ltd' are shown in Table 4
TABLE 4 quality index of four protein powders
As can be seen from Table 4, the protein powder using the chromium-removing ammonia-lowering agent was most significantly reduced in chromium content compared with the protein powder currently on the market. The literature reports that the chromium removal rate of the actual production by an alkaline method is about 95%, the total chromium removal rate of the chromium removal and ammonia reduction agent reaches 99.75%, and the chromium content of the product is far lower than the national standard; the chromium-removing ammonia-reducing agent is used for greatly reducing the ammonia content, improving the freshness of the protein powder and improving the quality of the protein powder; other qualities of the protein powder are also improved: the ash content is reduced, the fluffiness is increased, and the medium-speed solubility in water is also greatly improved. This is because the reduction of chromium reduces the chelation between protein molecules to increase the bulk and the quick solubility of the protein powder; the electrostatic adsorption material is coordinated with part of calcium ions in the solution to reduce ash content of protein powder.
The protein content determination method comprises the following steps: kjeldahl method.
The method for measuring the pH value of the solution comprises the following steps: a pH meter.
The method for measuring the ammonia content comprises the following steps: nahner reagent spectrophotometry.
Method for testing the instant solubility: 10g of collagen was taken at room temperature, 50mL of water was added, and the solution was stirred with a glass rod until the time required for clarification of the solution.
The chromium content measuring method comprises the following steps: 0.5g of collagen is weighed, a sample is decomposed by a dry ashing method, and the chromium content is measured by an atomic absorption spectrometer.
Ash content determination method: accurately weighing 5.000g of collagen, ashing on an electric furnace until no smoke appears, transferring to a muffle furnace, calcining at 550 ℃ for 4 hours, weighing until the weight is constant, and obtaining the ash content.
Bulk density measurement method: 50.00g of collagen was weighed into a measuring cylinder, the volume thereof was measured, and then the bulk density was obtained by dividing the mass by the volume.
The invention relates to an industrial grade material such as a coupling agent, which can be tried out by enterprises with the same functions.
Claims (4)
1. The chromium-removing ammonia-reducing agent for the chromium-containing collagen solution is characterized by comprising a chromium ion replacement material, an electrostatic adsorption material, an ammonia-reducing material, a magnetic material and a coating material, wherein the weight ratio of the five materials is 100:95-105:1000-1200:90-110:50-60;
wherein, the preparation method of the chromium ion replacement material comprises the following steps:
a 1 ) Nano SiO 2 Preparation of pellets: 25-30 mL of deionized water, 65-85 mL of absolute ethyl alcohol, 15-20 mL of ammonia water are mixed and heated to constant temperature in an oil bath at 35-40 ℃, 0.8g of 99% ethyl orthosilicate is dropwise added under strong stirring, the violent stirring reaction is continued for 30-40 min, a silica sphere seed solution is obtained, then 6.2g of ethyl orthosilicate is dropwise added, the reaction is continued for 2-3 h, and finally the nano SiO is obtained through centrifugal drying 2 A pellet;
b 1 ) Nano SiO 2 Preparation of APTES: 10g of step a 1 ) Nano SiO of (2) 2 The pellets are dispersed in 80-100 mL of absolute ethyl alcohol and uniformly dispersed by ultrasonic, so as to obtain nano SiO 2 Adding 60-80 mL of absolute ethyl alcohol and 25-35 mL of deionized water into a two-necked flask respectively, adding a trace amount of glacial acetic acid to adjust the pH to be 5-6, dropwise adding 2-4 mL of silane coupling agent KH-550 into the flask, fully stirring for hydrolysis, and then adding nano SiO 2 The pellet suspension was added dropwise to the flask and reacted at room temperature 1824-h, centrifuging the reaction solution, washing and centrifuging the reaction solution by 25mL of absolute ethyl alcohol, 15mL of absolute tetrahydrofuran and 15mL of acetone respectively, dispersing the solid by 30mL of deionized water, and freeze-drying to obtain a white solid product, namely the product nano SiO 2 -APTES；
c 1 ) Preparation of alpha-bromocitric acid: adding 10g of citric acid, 80-100 mL of absolute ethyl alcohol, 0.1-0.4 g of bromosuccinimide catalyst, heating to 65-75 ℃, dropwise adding 18-22 mL of bromine, after the dropwise adding is finished, preserving heat for 3-4 h at 65-75 ℃, and distilling under reduced pressure to remove redundant bromine, hydrogen bromide and ethanol to obtain alpha-bromocitric acid;
d 1 ) Preparation of alpha-bromomalonic acid: adding 10mL of malonic acid, 80-100 mL of absolute ethyl alcohol, adding 0.1-0.3 g of bromosuccinimide serving as a catalyst, heating to 65-75 ℃, dropwise adding 17-19 mL of bromine, preserving heat for 3-4 h at 65-75 ℃ after the dropwise adding is finished, and distilling under reduced pressure to remove redundant bromine, hydrogen bromide and ethanol to obtain alpha-bromomalonic acid;
e 1 ) Chromium ion replacement material, namely SiO 2 Preparation of APTES-PC/CA: adding 60-80 mL deionized water into a three-necked flask, and adding 4g of the deionized water in the step c 1 ) Alpha-bromocitric acid of (2) and 2-3 g of step d) 1 ) The alpha-bromomalonic acid is put into a three-necked bottle, 0.2 to 0.3g of potassium carbonate is added, and the mixture is heated to constant temperature in an oil bath at 30 to 40 ℃ and fully stirred for 10 to 20 minutes; slowly adding 20-30 g of step b 1 ) Nano SiO of (2) 2 APTES, refluxing for 2-3 h under magnetic stirring, suction filtering, washing with water, drying, grafting on nano SiO 2 The amino on the surface and the alpha-bromomalonic acid and the alpha-bromocitric acid undergo Huffman alkylation reaction to obtain a chromium ion replacement material, namely SiO 2 -APTES-PC/CA；
The carrier is one of kaolinite, montmorillonite, diatomite and magnesium silicate, and one of the carriers is selected and obtained through a series of modification;
a 2 ) Carrying out carrier activation treatment; weighing 40g of one of the carriers, adding 400mL 0.75~1.25moL/L hydrochloric acid solution, performing ultrasonic dispersion for 20-30 min, and reacting at 60-80 DEG CFiltering, washing to be neutral and drying for 5-6 hours to obtain an activated carrier;
b 2 ) 20g of step a) is added into a three-neck flask containing 80-100 mL of toluene 2 ) Under the protection of nitrogen flow of 60-80 mL/min, slowly raising the temperature of the mixed solution to 105-110 ℃, adding 3-5 g of 3-aminopropyl triethoxysilane, continuously stirring for 12-15 h, filtering, washing, purifying for 12-15 h by using absolute ethyl alcohol, and vacuum drying for 12-15 h at 70-80 ℃ to obtain an activated carrier-APTES;
c 2 ) Under the protection of nitrogen, 50-60 mL of dichloromethane and 0.025-0.035 mol of EDTA are removed, 2-3 mL of thionyl chloride is dropwise added at constant pressure, and 1g of step b is rapidly added 2 ) The activated carrier-APTES of the electrostatic adsorption material is reacted for 2-3 hours at room temperature, filtered, washed by 8mL of dichloromethane, 8mL of acetone, 10mL of deionized water, 10mL 0.15~0.25 moL/L of sodium bicarbonate aqueous solution and 10mL of deionized water, and dried at 50-60 ℃ to obtain the electrostatic adsorption material;
the preparation method of the ammonia-reducing material comprises the following steps:
a 3 ) Weighing 6.5~7.5g KOH,6.5g Al 2 (SO 4 ) 3 ·18H 2 3.5-4.0 g of 10nm granular graphene oxide is added into a beaker containing 600-650 mL of deionized water in sequence under the stirring state, and the mixture is stirred for 30-40 min to obtain A 1 A solution;
b 3 ) Weighing 500-550 mL of absolute ethyl alcohol, slowly adding 183g of ethyl orthosilicate in a beaker under strong stirring, and continuously stirring for 30-40 min after the dripping is finished to obtain B 1 A solution;
c 3 ) Under stirring, B is 1 Slowly adding the solution to A 1 Continuously stirring the solution for 60-70 min after the solution is added;
d 3 ) Step c 3 ) Transferring the obtained solution into a reaction kettle with a polytetrafluoroethylene lining, reacting in an oven at 165-175 ℃ for 40-50 h, washing the product to be neutral by deionized water after the reaction is finished, and drying in the oven at 90-100 ℃;
e 3 ) Placing the dried product in a muffle furnace for roasting at 540-580 ℃ for 20-2Obtaining zeolite after 5 hours;
f 3 ) Zeolite activation treatment, step e 3 ) Placing the product in 500mL 0.8~1.4 moL/L NaCl solution, reacting for 8-12 hours in a water bath constant temperature shaking box at 30-45 ℃, washing with deionized water, and drying to obtain an ammonia-reducing material;
the preparation method of the magnetic material comprises the following steps:
a 4 ) Adding 20-30 mL of deionized water into 70-80 mL of ethylene glycol, stirring, adding 32.0g of isobutylamine and 6.0-7.0 g of diethanolamine, and stirring for 5-10 min to obtain A 2 A solution;
b 4 ) 3.0g FeCl 2 .4H 2 O is dissolved in 30-40 mL of deionized water, 60-70 mL of ethylene glycol is added, and B is obtained by stirring while adding 2 A solution;
c 4 ) Adding 20-30 mL of deionized water into 70-80 mL of ethylene glycol, and adding 5.0g of FeCl 3 .6H 2 O, stirring for 5min to obtain C 2 A solution;
d 4 ) Will A 2 The solution is divided into two parts, one part is combined with B 2 Mixing the solution, and mixing one part with C 2 Mixing the solutions;
e 4 ) Mixing and stirring two parts of mixed solution for 20-30 min, pouring the mixed solution into a polyimide lining, covering, sealing by using an adhesive tape, placing the lining into an oven at 90-100 ℃, keeping the temperature for 5-10 h, naturally cooling to room temperature, separating a black product by using a magnet, washing with 100-150 mL of ionized water, washing with 100-150 mL of absolute ethyl alcohol for 2-4 times, and placing the lining into the oven at 30-40 ℃ for drying for 6-12 h to obtain the magnetic material ferroferric oxide;
the coating material is one or more of hydroxymethyl cellulose, carboxymethyl cellulose, polyacrylamide/polyethyleneimine.
2. The chromium-removing ammonia-reducing agent according to claim 1, wherein 100g of chromium ion replacement material and 95-105 g of electrostatic adsorption material, 1000-1200 g of ammonia-reducing material and 95-105 g of magnetic material are poured into a three-necked bottle, and stirred at normal temperature for 30-40 min; spraying 2000-2400 mL of water to dissolve 50-60 g of coating material into a three-necked bottle while stirring, then placing the product obtained by the operation into a blast drier for drying, firstly drying at 70-80 ℃ for 1h, then heating to 110-115 ℃ for 1-1.5 h, and drying to obtain the chromium and ammonia removal agent.
3. Use of the chromium-removing ammonia-reducing agent according to claim 1 in a chromium-containing collagen solution, characterized by the following operative steps: weighing 1L of a collagen solution with 20.6mg/L of chromium content, 203g/L of collagen content, 9 of pH value and 200mg/L of ammonia content into a three-necked bottle, adjusting the pH value to 10.5-11.5 by alkali, adding 12-18 g of the chromium and ammonia removal agent of claim 1, stirring at the reaction temperature of 60-90 ℃ for reacting for 2-3 hours, adding sulfuric acid for adjusting the pH value of the solution to 6-7, continuously stirring for 2.5-3.5 hours, stopping processing and standing, adding a magnet under the three-necked bottle, and realizing solid-liquid rapid separation by utilizing the magnetic effect and natural sedimentation effect, thereby obtaining the collagen solution and chromium slag by a decantation method.
4. The use of chromium-removing ammonia-lowering agent according to claim 3 in chromium-containing collagen solution, wherein the alkali used is one or more of sodium hydroxide, potassium carbonate, sodium carbonate, calcium oxide, magnesium oxide, and calcium hydroxide.
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