CN102875406B - Special composite mimic enzyme for advanced treatment of pulping and paper-making waste water, and preparation method and application thereof - Google Patents
Special composite mimic enzyme for advanced treatment of pulping and paper-making waste water, and preparation method and application thereof Download PDFInfo
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- CN102875406B CN102875406B CN201210393644.2A CN201210393644A CN102875406B CN 102875406 B CN102875406 B CN 102875406B CN 201210393644 A CN201210393644 A CN 201210393644A CN 102875406 B CN102875406 B CN 102875406B
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Abstract
The invention relates to a special composite mimic enzyme for the advanced treatment of pulping and paper-making waste water, and a preparation method and application of the special composite mimic enzyme. The special composite mimic enzyme is prepared by the method comprising the following steps of: dissolving ferrous sulfate heptahydrate into distilled water to prepare 10-25% solution; controlling the temperature of the solution to be 20-35 DEG C; adding ethylene diamine tetraacetic acid tetrasodium into the solution according to the proportion under the stirring condition; and stirring for reaction for 25-40min to obtain the special composite mimic enzyme. The composite mimic enzyme is mild in reaction conditions and simple in technology, is used for the advanced treatment of the pulping and paper-making waste water, and is less in adding amount, high in catalysis efficiency, good in treatment effect and low in treatment cost.
Description
Technical field
The present invention relates to imitative enzyme of a kind of waste water advanced processing specific complex and preparation method thereof and application, especially a kind of effectively for the imitative enzyme of the paper-making effluent advanced treatment specific complex after secondary biochemical treatment.
Background technology
Through the paper-making effluent of secondary biochemical treatment, its remaining principal pollutant are xylogen and biochemical derivative thereof, and it is the key that realizes paper-making effluent advanced treatment that the solvability lignin material in paper-making effluent is effectively removed.At present, paper-making effluent advanced treatment technology mainly contains flocculation-air floating or precipitation technology, high-level oxidation technology, adsorption filtration technology, membrane filtration technique, Ecological Disposal technology etc.The more paper-making effluent advanced treatment process of application is Fenton oxidizing process at present.Fenton oxidizing process is to be OH by ferrous ion decomposition of hydrogen peroxide under lower pH condition, and the OH with stronger oxidation capacity is CO by the organic pollutant exhaustive oxidation in waste water
2thereby, realizing useless water purification, the essence of reaction is that pollutent is transferred to gas phase from liquid phase.The feature of Fenton oxidizing process is that the pH of reaction process control is high compared with high (505 ~ 520mV), hydrogen peroxide consumption alkali number large, that readjustment basicity needs compared with ORP low, reaction process, simultaneously, because reaction system has higher oxidizing potential, water outlet is with significantly light yellow.The method need to be added a large amount of chemical reagent equally, and processing cost is high.CN102398933A(CN201010280206.6) disclose a kind of leather making waste water treatment agent, by calcium hydroxide, polyacrylamide, ferrous sulfate, alum, formed.
Imitative enzyme is from natural enzyme, to pick out more active factors, as: active sites, hydrophobic microenvironment, with the multiple non-covalent interaction of substrate and synergistic effect thereof etc., in order to design the synthetic excellent properties that can show enzyme, nonprotein molecule or the molecular aggregate simple, more stable than enzyme, simulates natural enzyme to the identification of substrate, combination and katalysis again.The research of imitative enzyme is one of study hotspot of modern bionics and Green Chemistry.
In the more imitative enzyme of pulping and paper-making area research, great majority are the organic coordination compounds of simulating the transition metal of the native catalase such as LiP, MnP or Lac on molecular structure, the ligand of these imitative enzymes mainly contains porphyrin, phthalocyanine, schiff bases, amine etc., and central ion generally comprises the transition element such as iron, copper, aluminium, cobalt.Because the high price of the ligand such as porphyrin, phthalocyanine, the central ions such as copper, cobalt, manganese are heavy metal ion, and price is high and to have the factors such as secondary pollution, iron be that compound imitative enzyme is having superiority aspect paper-making effluent advanced treatment.
At present, at the more imitative enzyme of iron system of pulping and paper-making area research, mainly contain: iron porphyrin, ferrous sulfate, iron trichloride, Fe-EDTA, Fe-salen and protoheme etc.The imitative enzyme system of above iron system, catalytic efficiency is low, specificity is poor (ferrous sulfate, iron trichloride) for existing of having; There is the problems such as more expensive, the synthetic difficulty of part price (Fe-EDTA, Fe-salen, iron porphyrin, protoheme) in what have.Therefore, the imitative enzyme large-scale application in paper-making effluent advanced treatment of above monomer still has certain limitation.
Summary of the invention
For the deficiencies in the prior art part, the invention provides a kind of paper-making effluent advanced treatment specific complex with low cost, that catalytic efficiency is high and imitate enzyme and preparation method thereof, preparation technology of the present invention is simple.The present invention also provides the application of this compound imitative enzyme.
Technical solution of the present invention is as follows:
Paper-making effluent advanced treatment specific complex is imitated an enzyme, and the imitative enzyme of this specific complex makes by the following method:
Ferrous sulfate is dissolved in distilled water, be made into ferrous sulfate mass concentration and be 10 ~ 25% solution, then control solution temperature at 20 ~ 35 ℃, under agitation condition, in solution, add tetrasodium ethylenediamine tetraacetate, the mol ratio of described tetrasodium ethylenediamine tetraacetate and ferrous sulfate is 1:10 ~ 25, and preferred tetrasodium ethylenediamine tetraacetate and ferrous sulfate be 1:15 ~ 20 in molar ratio; Stirring reaction 25 ~ 40min after adding, obtains the imitative enzyme of specific complex.
Preferred according to the present invention, described tetrasodium ethylenediamine tetraacetate and ferrous sulfate are 1:15 ~ 20 in molar ratio.
Preferred according to the present invention, the mass concentration of described ferrous sulfate solution is 15 ~ 20%.
Preferred according to the present invention, described control solution temperature is at 23 ~ 25 ℃.
The imitative enzyme of specific complex of the present invention is used for paper-making effluent advanced treatment.
While adopting the imitative enzyme of specific complex of the present invention to paper-making effluent advanced treatment, to the described compound imitative enzyme that adds 1 ~ 1.4mmol/L in waste water, mole number is with Fe
2+ionometer.Can significantly reduce the COD of water after processing
crvalue and colourity.
The element ratio of the compound imitative enzyme system of the present invention provides enough metal ions for the complex-precipitation of waste water advanced treating processes catalytic reaction products simultaneously, the effect of the paper-making effluent advanced treatment effectively guaranteeing.Adopt the imitative enzyme advanced treatment paper-making effluent of specific complex of invention, catalyzed reaction principle is, compound imitative enzyme catalysis hydrogen peroxide generates hydroxyl free radical, hydroxyl free radical oxidized waste organic pollutants (xylogen and biochemical derivative thereof) makes it carboxylated, the free Fe in carboxylated organic pollutant and compound imitative enzyme
2+complexing generates has the catalyzer that catalyzing hydrogen peroxide generates hydroxyl free radical function equally, realizes catalytic cycle.Along with the increase of the carboxylated degree of Organic Pollutants in Wastewater, the catalysate Fe of compound imitative enzyme
3+with the carboxyl generation complex reaction of the reaction product of Organic Pollutants in Wastewater, generate water-soluble poor organic carboxyl acid iron precipitation, then by solid-liquid separation means, realize purification of waste water, reach the object of paper-making effluent advanced treatment.
It is that main raw material, a small amount of tetrasodium ethylenediamine tetraacetate are batching that the present invention adopts cheap ferrous sulfate, and under mild conditions, the imitative enzyme of cheap specific complex is prepared in reaction; Due to excessive Fe
2+react with tetrasodium ethylenediamine tetraacetate and generate ethylenediamine tetraacetic acid (EDTA)-ferrous complex Fe-EDTA, therefore this compound imitative enzyme system is organically blending of ferrous sulfate and two kinds of imitative enzyme systems of Fe-EDTA, efficiently solves the low and imitative higher difficult problem that limits its application of enzyme price of Fe-EDTA of the imitative enzyme catalysis efficiency of ferrous sulfate.The imitative enzyme of paper-making effluent advanced treatment specific complex of the present invention and application art thereof are compared with existing technique, have following characteristics: one, compound imitative enzyme raw materials kind is few, cheap and easy to get; Two, compound imitative enzyme raw materials stable in properties, nontoxic, processes waste water and can not cause secondary pollution; Three, compound imitative enzyme preparation feedback mild condition, technique is simple, and catalytic efficiency is high; Four, compound imitative enzyme advanced treatment paper-making effluent of the present invention, it is few that compound imitative enzyme adds dosage, and treatment effect is good, and processing costs is low.Use this compound imitative enzyme, compare cost 50-60% with using the imitative enzyme of Fe-EDTA.
Embodiment
Below by specific embodiment, the present invention is described in further details.
Embodiment 1:
Ferrous sulfate is dissolved in distilled water, the mass concentration of ferrous sulfate is 20%, then control solution temperature at 25 ℃, under agitation condition, in solution, slowly add tetrasodium ethylenediamine tetraacetate, the tetrasodium ethylenediamine tetraacetate adding and the mol ratio of ferrous sulfate are 1:15, stirring reaction 30min after adding, mixing solutions is the imitative enzyme of specific complex.
Applicating example: poplar be take as raw material, with chemical pulping, the enterprises in pulp and paper industry second pond water outlet of producing Cultural Paper, COD in Shandong
crfor 368mg/L, colourity is 400 times, and pH is 7.8.Adopt imitative this paper-making effluent of enzyme advanced treatment of specific complex of embodiment 1, to adding the compound imitative enzyme of 1.08mmol/L in waste water, (mole number is with Fe
2+ionometer) waste water index is COD and after other conventional dose (other conventional dose: vitriol oil 150mg/L, hydrogen peroxide 200mg/L, lime 150mg/L, aluminum chloride 50mg/L, polyacrylamide 2mg/L) advanced treatment
crfor 42mg/L, colourity is 8 times.
Embodiment 2:
Ferrous sulfate is dissolved in distilled water, the mass concentration of ferrous sulfate is 15%, then control solution temperature at 23 ℃, under agitation condition, in solution, slowly add tetrasodium ethylenediamine tetraacetate, the tetrasodium ethylenediamine tetraacetate adding and the mol ratio of ferrous sulfate are 1:20, stirring reaction 30min after adding, mixing solutions is the imitative enzyme of specific complex.
Applicating example: take waste paper and be raw material, the enterprises in pulp and paper industry second pond water outlet of producing newsprinting paper, COD in Shandong
crfor 146mg/L, colourity is 200 times, and pH is 7.3.Adopt imitative this paper-making effluent of enzyme advanced treatment of specific complex of embodiment 2, to adding the compound imitative enzyme of 1.18mmol/L in waste water, (mole number is with Fe
2+ionometer) and other medicaments (vitriol oil 180mg/L, hydrogen peroxide 200mg/L, lime 160mg/L, aluminum chloride 50mg/L, polyacrylamide 2mg/L), after advanced treatment, waste water index is COD
crfor 38mg/L, colourity is 5 times.
Embodiment 3:
Ferrous sulfate is dissolved in distilled water, the mass concentration of ferrous sulfate is 20%, then control solution temperature at 25 ℃, under agitation condition, in solution, slowly add tetrasodium ethylenediamine tetraacetate, the tetrasodium ethylenediamine tetraacetate adding and the mol ratio of ferrous sulfate are 1:20, stirring reaction 30min after adding, mixing solutions is the imitative enzyme of specific complex.
Applicating example: wheat straw be take as raw material, with half chemical pulping, the enterprises in pulp and paper industry second pond water outlet of producing boxboard, COD in Shandong
crfor 455mg/L, colourity is 500 times, and pH is 7.7.Adopt imitative this paper-making effluent of enzyme advanced treatment of specific complex of embodiment 3, to adding the compound imitative enzyme of 1.30mmol/L in waste water, (mole number is with Fe
2+ionometer) and other medicaments (vitriol oil 120mg/L, hydrogen peroxide 200mg/L, lime 140mg/L, aluminum chloride 50mg/L, polyacrylamide 2mg/L), after advanced treatment, waste water index is COD
crfor 44mg/L, colourity is 5 times.
Claims (5)
1. pulp and paper effluent treatment specific complex is imitated an enzyme, it is characterized in that the imitative enzyme of this specific complex makes by the following method:
Ferrous sulfate is dissolved in distilled water, be made into ferrous sulfate mass concentration and be 10 ~ 25% solution, then control solution temperature at 20 ~ 35 ℃, under agitation condition, in solution, add tetrasodium ethylenediamine tetraacetate, the mol ratio of described tetrasodium ethylenediamine tetraacetate and ferrous sulfate is 1:10 ~ 25; Stirring reaction 25 ~ 40min after adding, obtains the imitative enzyme of specific complex.
2. the imitative enzyme of specific complex as claimed in claim 1, is characterized in that described tetrasodium ethylenediamine tetraacetate and ferrous sulfate are 1:15 ~ 20 in molar ratio.
3. specific complex as claimed in claim 1 is imitated enzyme, and the mass concentration that it is characterized in that described ferrous sulfate solution is 15 ~ 20%.
4. the imitative enzyme of specific complex as claimed in claim 1, is characterized in that described control solution temperature is at 23 ~ 25 ℃.
5. the application of the imitative enzyme of the specific complex described in claim 1 ~ 4 any one, for to pulp and paper effluent treatment, to the described compound imitative enzyme that adds 1 ~ 1.4mmol/L in waste water, mole number is with Fe
2+ionometer.
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| CN110785524B (en) * | 2017-06-29 | 2022-09-06 | 凯米拉公司 | Composition for removing and preventing wet strength resin contaminants in papermaking equipment, use thereof and method |
| CN110723869B (en) * | 2019-10-09 | 2021-07-02 | 合肥停弦渡生物科技有限公司 | Improved Fenton sewage treatment method based on pre-oxidant |
| CN110684750A (en) * | 2019-10-09 | 2020-01-14 | 合肥停弦渡生物科技有限公司 | Preparation method of auxiliary enzyme preparation for sewage treatment |
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Non-Patent Citations (7)
| Title |
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| Colleen. C. Walker等.evaluating three iron-based biomimetic compounds for their selectivity in a polymeric model system for pulp.《Tappi Journal》.1995,第78卷(第6期),103-109. |
| evaluating three iron-based biomimetic compounds for their selectivity in a polymeric model system for pulp;Colleen. C. Walker等;《Tappi Journal》;19950630;第78卷(第6期);103-109 * |
| Fe-CA仿酶-混凝法处理麦草化机浆综合废水的研究;高洪贵等;《中国造纸学报》;20091230;第24卷(第1期);68-71 * |
| Technology》.2008,第27卷(第3期),10-13. * |
| 高洪贵等.Fe-CA仿酶-混凝法处理造纸综合废水.《Paper Science & Technology》.2008,第27卷(第3期),10-13. |
| 高洪贵等.Fe-CA仿酶-混凝法处理造纸综合废水.《Paper Science & * |
| 高洪贵等.Fe-CA仿酶-混凝法处理麦草化机浆综合废水的研究.《中国造纸学报》.2009,第24卷(第1期),68-71. |
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Address after: 250013 Lishan Road, Lixia District, Ji'nan, Shandong, 50 Patentee after: Shandong Environmental Protection Scientific Research Design Institute Co., Ltd. Address before: 250013 Lishan Road, Lixia District, Ji'nan, Shandong, 50 Patentee before: Shandong Academy of Environmental Science |
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Effective date of registration: 20211229 Address after: 251600 east of Yukai Road, north of Keyuan street, Shanghe County Economic Development Zone, Jinan City, Shandong Province Patentee after: New kinetic energy environmental protection service branch of Shandong Environmental Protection Research and Design Institute Co.,Ltd. Address before: 250013 No. 50 Lishan Road, Lixia District, Shandong, Ji'nan Patentee before: SHANDONG ACADEMY OF ENVIRONMENTAL SCIENCES Co.,Ltd. |