CN102875406A - 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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- CN102875406A CN102875406A CN2012103936442A CN201210393644A CN102875406A CN 102875406 A CN102875406 A CN 102875406A CN 2012103936442 A CN2012103936442 A CN 2012103936442A CN 201210393644 A CN201210393644 A CN 201210393644A CN 102875406 A CN102875406 A CN 102875406A
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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 imitating enzyme through the paper-making effluent advanced treatment specific complex after the 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 the paper-making effluent advanced treatment that the solvability lignin material in the 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.Using more paper-making effluent advanced treatment process at present is the Fenton oxidizing process.The 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 with the organic pollutant exhaustive oxidation in the waste water
2Thereby, realizing the purification of waste water, the essence of reaction is that pollutent is transferred to gas phase from liquid phase.The characteristics of Fenton oxidizing process be the pH ORP lower, reaction process of reaction process control higher (505 ~ 520mV), hydrogen peroxide consumption alkali number large, that readjustment basicity needs is high, 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, formed by calcium hydroxide, polyacrylamide, ferrous sulfate, alum.
Imitative enzyme is to pick out more active factors from natural enzyme, 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 simulated natural enzyme to identification, combination and the katalysis of substrate 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 at 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 have the factors such as secondary pollution, and iron is that compound imitative enzyme is having superiority aspect the paper-making effluent advanced treatment.
At present, mainly contain at the more imitative enzyme of iron system of pulping and paper-making area research: iron porphyrin, ferrous sulfate, iron trichloride, Fe-EDTA, Fe-salen and protoheme etc.The imitative enzyme system of above iron system, existing of having, catalytic efficiency was low, specificity is poor (ferrous sulfate, iron trichloride); What have exists more expensive, the synthetic difficulty of part price problems such as (Fe-EDTA, Fe-salen, iron porphyrin, protohemes).Therefore, the imitative enzyme large-scale application in the 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 this compound imitative application of enzymes.
Technical solution of the present invention is as follows:
A kind of paper-making effluent advanced treatment specific complex is imitated enzyme, and the imitative enzyme of this specific complex makes by the following method:
Ferrous sulfate is dissolved in the distilled water, be made into the 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; Add complete rear stirring reaction 25 ~ 40min, namely get 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 the paper-making effluent advanced treatment.
When adopting the imitative enzyme of specific complex of the present invention to the paper-making effluent advanced treatment, add the described compound imitative enzyme of 1 ~ 1.4mmol/L in the 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 the metal ion of capacity simultaneously for the complex-precipitation of waste water advanced treating processes catalytic reaction products, the effect of the paper-making effluent advanced treatment that effectively guarantees.Adopt the imitative enzyme advanced treatment paper-making effluent of specific complex of invention, the 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 the compound imitative enzyme
2+Complexing generates has the catalyzer that catalyzing hydrogen peroxide generates the 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 relatively poor organic carboxyl acid iron precipitation, again by solid-liquid separation means, realize purification of waste water, reach the purpose 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 the imitative enzyme of cheap specific complex is prepared in reaction under mild conditions; Because excessive Fe
2+Generate ethylenediamine tetraacetic acid (EDTA)-ferrous complex Fe-EDTA with the tetrasodium ethylenediamine tetraacetate reaction, 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 efficient 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, and 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 is 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 the 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 that adds and the mol ratio of ferrous sulfate are 1:15, add complete rear stirring reaction 30min, mixing solutions is the imitative enzyme of specific complex.
Applicating example: Shandong is take poplar as raw material, with chemical pulping, the enterprises in pulp and paper industry second pond water outlet of producing Cultural Paper, COD
CrBe 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, (mole number is with Fe to add the compound imitative enzyme of 1.08mmol/L in the waste water
2+Ionometer) the 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
CrBe 42mg/L, colourity is 8 times.
Embodiment 2:
Ferrous sulfate is dissolved in the 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 that adds and the mol ratio of ferrous sulfate are 1:20, add complete rear stirring reaction 30min, mixing solutions is the imitative enzyme of specific complex.
Applicating example: Shandong take waste paper as raw material, the enterprises in pulp and paper industry second pond water outlet of producing newsprinting paper, COD
CrBe 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, (mole number is with Fe to add the compound imitative enzyme of 1.18mmol/L in the waste water
2+Ionometer) and other medicaments (vitriol oil 180mg/L, hydrogen peroxide 200mg/L, lime 160mg/L, aluminum chloride 50mg/L, polyacrylamide 2mg/L), the waste water index is COD after the advanced treatment
CrBe 38mg/L, colourity is 5 times.
Embodiment 3:
Ferrous sulfate is dissolved in the 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 that adds and the mol ratio of ferrous sulfate are 1:20, add complete rear stirring reaction 30min, mixing solutions is the imitative enzyme of specific complex.
Applicating example: Shandong is take wheat straw as raw material, with half chemical pulping, the enterprises in pulp and paper industry second pond water outlet of producing boxboard, COD
CrBe 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, (mole number is with Fe to add the compound imitative enzyme of 1.30mmol/L in the waste water
2+Ionometer) and other medicaments (vitriol oil 120mg/L, hydrogen peroxide 200mg/L, lime 140mg/L, aluminum chloride 50mg/L, polyacrylamide 2mg/L), the waste water index is COD after the advanced treatment
CrBe 44mg/L, colourity is 5 times.
Claims (5)
1. a paper-making effluent advanced treatment specific complex is imitated enzyme, it is characterized in that the imitative enzyme of this specific complex makes by the following method:
Ferrous sulfate is dissolved in the distilled water, be made into the 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; Add complete rear stirring reaction 25 ~ 40min, namely get 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 imitative application of enzymes of each described specific complex of claim 1 ~ 4 is used for the paper-making effluent advanced treatment, adds the described compound imitative enzyme of 1 ~ 1.4mmol/L in the waste water, and mole number is with Fe
2+Ionometer.
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| CN201210393644.2A CN102875406B (en) | 2012-10-16 | 2012-10-16 | Special composite mimic enzyme for advanced treatment of pulping and paper-making waste water, and preparation method and application thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN110723869A (en) * | 2019-10-09 | 2020-01-24 | 合肥停弦渡生物科技有限公司 | Improved Fenton sewage treatment method based on pre-oxidant |
| CN110785524A (en) * | 2017-06-29 | 2020-02-11 | 凯米拉公司 | Composition for removing and preventing wet strength resin contaminants in papermaking equipment, use thereof and method |
-
2012
- 2012-10-16 CN CN201210393644.2A patent/CN102875406B/en active Active
Non-Patent Citations (3)
| Title |
|---|
| COLLEEN. C. WALKER等: "evaluating three iron-based biomimetic compounds for their selectivity in a polymeric model system for pulp", 《TAPPI JOURNAL》 * |
| 高洪贵等: "Fe-CA仿酶-混凝法处理造纸综合废水", 《PAPER SCIENCE & TECHNOLOGY》 * |
| 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》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110785524A (en) * | 2017-06-29 | 2020-02-11 | 凯米拉公司 | Composition for removing and preventing wet strength resin contaminants in papermaking equipment, use thereof and method |
| 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 |
| 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 |
| CN110723869A (en) * | 2019-10-09 | 2020-01-24 | 合肥停弦渡生物科技有限公司 | Improved Fenton sewage treatment method based on pre-oxidant |
| 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 |
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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. |