CN102887581B - Flocculating agent for treating sewage in Chinese patent medicine production enterprises and preparation method thereof - Google Patents
Flocculating agent for treating sewage in Chinese patent medicine production enterprises and preparation method thereof Download PDFInfo
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- CN102887581B CN102887581B CN201210401772.7A CN201210401772A CN102887581B CN 102887581 B CN102887581 B CN 102887581B CN 201210401772 A CN201210401772 A CN 201210401772A CN 102887581 B CN102887581 B CN 102887581B
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Abstract
The invention discloses a flocculating agent for treating sewage in Chinese patent medicine production enterprises, wherein the flocculating agent comprises the following compositions: 30-45% of carapace crushed materials, 3-12% of modified chitosan, 0.05-0.5% of nanometer titanium dioxide, 0.1-0.5% of phytic acid, and 45-55% of zeolite; in order to optimize the effect, the flocculating agent is also added with 1-5% of white mica and 1-5% of active carbon. The flocculating agent provided by the invention is utilized to treat the sewage; the flocculating agent provided by the invention has very high efficiencies of removing COD (chemical oxygen demand) and BOD (biochemical oxygen demand); and the flocculating agent provided by the invention is efficient and economical.
Description
Technical field
The present invention relates to a kind of sewage treatment flocculating agent and preparation method thereof, be specifically applicable to the improvement of Chinese patent medicine manufacture sewage.
Background technology
The Chinese patent medicine it has often been said in life refers to by Chinese medicinal materials and makes by the principle formula of necessarily curing the disease, and the ready-made medicine that can take at any time, as various pills, powder, electuary etc.Advantage be ready-made available, adapt to be badly in need of, storage facilitates, can carry, saved decoction decoction process, eliminated Chinese herbs decoction distinctive peculiar smell and pessimal stimulation etc. while taking.
The production of Chinese patent medicine all can produce a large amount of waste water in raw material washing extract drugs and flushing process, has organic contamination substrate concentration high, and suspension content is high, and colourity is high, the unsettled feature of biodegradability.Make sewage through processing, can effect stably reach the emission standard that effluent quality meets environmental administration's requirement, have certain difficulty, use flocculation agent to remove the material that is wherein unfavorable for biochemical treatment, can reduce cost of sewage disposal, and be conducive to the recycling of mud after flocculation sediment.
Its source of Chinese patent medicine sewage is mainly that equipment rinses, medicinal material cleans, it is concentrated to extract and workshop is rinsed, and living facilities.Principal pollutant are natural organic matter, as water miscible carbohydrate, glycoside, Anthraquinones, tannin, organic acid, xylogen, alkaloid, tannin, protein, starch, grease etc., the pollutent of non-solubility mainly carrys out self-stip, extracts silt, the plant suspended substance of workshop section, and also having some is some heavy metal substances that exist in Chinese medicine.Facts have proved, some Chinese patent medicine factory effluent organic concentration is high, complicated component, and the feature that biodegradability is poor, in the debugging and use procedure of Practical Project, how to launch the Processing Technology Research of Chinese medicine sewage, and obtained good treatment effect, perplex many Chinese patent medicines enterprise always and further expand industrial scale.Particularly, during Chinese patent medicine is produced, because raw-material reason, there is the problem of heavy metal always, cause compatriots' concern always.
Chitosan is a kind of natural organic high-molecular compound, as water conditioner, industrial, widely applies, and the U.S. is mainly used in water treatment and drinking water treatment; Japan is mainly used in water treatment and sewage disposal, and wherein the chitosan for water treatment reaches 500 tons more than every year.Itself has no side effect chitosan, fully biodegradable, its structure is straight chain macromole, on molecule, contain a plurality of hydroxyls, amino isoreactivity group, the organism such as metal ion, dyestuff look ion, halogen, protein, amino acid and clay particle are had to good chemisorption, the good bactericidal ability of tool also can be used to prepare high-efficient low-toxicity multifunctional flocculation agent aspect water treatment simultaneously.
Chitosan (Chitosan, CHI) is a kind of natural polymers, can first by shrimp and crab shells, through diluted acid, diluted alkaline, process decalcification, deproteinization and fat and obtain similar in cellulosic chitin, and then in concentrated alkali solution, deacetylate obtains.Chitosan is a kind of high performance heavy metal capturing agent, this mainly has benefited from chitosan macromole and contains a large amount of amino, hydroxyl, the amino of chitosan, hydroxyl and heavy metal ion form stable five rings shape inner complex, make the superpolymer of the chitosan formation interlinkage of straight chain, heavy metal ion is had to good sequestering action, and it can remove the heavy metal ion such as copper in trade effluent, cadmium, mercury.Chitosan is environmentally friendly, and people utilize these characteristics of chitosan more and more, develop many purposes.Along with the carrying out of a large amount of fundamental and applied researchs in recent years, chitin and derivative thereof demonstrate its unique using value at numerous areas such as chemical industry, printing and dyeing, papermaking, medicine, food, environmental protection, a kind of natural macromolecule flocculating agent that has good development prospect, the Japan and other countries processing for urban domestic wastewater and trade effluent by it.
Summary of the invention
Existing problem in producing for Chinese patent medicine, the invention provides a kind of efficient and manageable biological activity flocculation agent using for Chinese patent medicine waste water.
For addressing the above problem, technical scheme is as follows:
This flocculation agent is mainly used in the pollutent that biochemical degradation Chinese patent medicine sewage is harmed in preliminary removal, so that sewage enters follow-up biochemical processing process.
Flocculation agent of the present invention comprises following component: 30-45% carapace powder particle, 3-12% modified chitosan, 0.05-0.5% nano titanium oxide, 0.1-0.5% phytic acid, 45-55% zeolite, 1-5% white mica, 1-5% gac.
Described gac is 10-30 order.
Described carapace powder particle is 500-1000 order, the environmental problem that cannot recycle for solving the crust that exists in current many aquaculture field, we have selected refuse shell to recycle especially, utilize superfine communication technique to carry out miniaturization to crust, studied the factor that affects crushing effect in crushing process, major control because have: the time, feeding, muller gap, wind-force etc., the granularity that makes target crust is 500-1000 object granularity.
500-1000 object carapace powder particle, be applicable to Chinese patent medicine sewage disposal, because the character of himself, is suitable for hydrolysis, and in its hydrolysis, can remove certain pollutent, therefore, its role is more special, in some Chinese patent medicine sewage, particularly highly acid Chinese patent medicine sewage, is particularly suitable for the flocculation sediment processing in its early stage.
The present invention also provides a kind of its preparation method of the flocculation agent for the waste water control of Chinese patent medicine manufacturing enterprise, and technical scheme is as follows:
Get 300-450g ultra micro carapace powder particle, modified chitosan 30g-120g, nano titanium oxide 0.5g-5g, stirs, and standingly makes the preliminary slaking of its character, makes batching 1; Get zeolite 450g-550g mixing and stirring, make batching 2; Finally batching 1 and batching 2 are mixed, mix on limit, and limit drips 1g-5g phytic acid, makes the flocculation agent of 1000g.
Described batching 2 also can add 1-5% white mica and 1-5% gac.
For chitosan in common pH(7～9 of waste water) flocculating effect is poor while using separately under condition, the present invention strengthens its stability and cationic properties by modification, improve its removal ability to the electronegativity particle in water body, make it to keep COD the efficient clearance of SS.
Described modified chitosan is with Fe
3+for properties-correcting agent, add micro-nano titanium oxide, and add Mg
2+, prepared chitosan complex ferric flocculant, described modified chitosan optimal preparation technology is: first chitosan is made to the aqueous solution, then with Fe
3+for properties-correcting agent and chitosan complex, then by regulating acidity to make to be hydrolyzed in right amount by the iron ion of complexing, the 0.01-0.15% that nano titanium oxide is total mass, the optimum quality ratio of chitosan and iron, magnesium is 6:2:1.The more former chitosan solution of prepared chitosan complex ferric flocculant acidity is low, and hydrolysis trend weakens greatly, and the stability of solution strengthens greatly.With standard method, tested the flocculating property of chitosan complex iron to waste water, shown when pH=7, flocculating effect (rate of descent) is 92.56%, and has and do not need to regulate waste water acidity, go out the features such as acidity of water is substantially constant.
The present invention has following beneficial effect:
1, Chinese patent medicine pharmacy waste water complicated component, is difficult for reclaiming, and recovery process is complicated, and cost is higher.And also there is no at present the special sewage-treating agent for Chinese patent medicine factory effluent, a medicament of particularly carrying out a biological disposal upon.Biological flocculant of the present invention is that specific aim is processed Chinese patent medicine factory effluent.Because biological flocculant energy specific aim of the present invention is processed the current ubiquitous heavy metal pollution problem of Chinese patent medicine, chitosan has well been processed this difficult problem of heavy metal adsorption, and the crust after pulverizing, itself contain some polymers, be easy in Chinese patent medicine sewage, better be hydrolyzed or adsorb corresponding hazardous and noxious substances, simultaneously, problem for existing many hardly-biodegradables in Chinese patent medicine sewage, also can be along with the later stage filters, produce good effect, make sewage have more biodegradability.
2, biological activity flocculation agent of the present invention, introduce the crust after chitosan and micronizing, and appropriateness adopted conventional technique, by its organic adsorptive power, better solve effluent problem, simultaneously also reduced simple use chitosan and the problem of the high cost that causes.And biological activity flocculation agent of the present invention can also recycle, after being filtered dry, can be used for agriculture production base nutritive element additive or be directly used in reclaiming contained special high value metals in some Chinese patent medicine starting material, as copper etc.
3, conventional sorbent material has gac, active coal, humic acids, polymeric adsorbent etc., and the present invention, on conventional sorbent material basis, has added phytic acid, has further improved adsorptive power.
Embodiment
Below in conjunction with embodiment, further set forth technical scheme of the present invention, but be not limited to the following examples.
Embodiment 1
1) get 1000 order ultra micro carapace powder particle 445g, modified chitosan 50g, nano titanium oxide 0.5g, stirs, and standing 0.5 hour, make the preliminary slaking of its character, make batching 1;
2) get white clouds master slice 30g, 10 order gac 20g, 30 order zeolite 450g mixing and stirring, make batching 2;
3) finally step 1 and step 2 are made to batching and mix, mix on limit, and limit drips 4.5g phytic acid, makes the flocculation agent of 1000g.
The flocculation agent of this proportioning preparation, is applied to certain Chinese patent medicine sewage disposal, and the COD of sewage discharge waste water is 3250-4120mg/L, flocculation sediment through enough flocculation agents, and in conjunction with conventional Air Exposure, COD water outlet is 147.3mg/L, can reach COD clearance more than 95.5-96.5%.
Embodiment 2
1) get 1000 order ultra micro carapace powder particle 320g, modified chitosan 70g, nano titanium oxide 2g, stirs, and standing 1.5 hours, make the preliminary slaking of its character, make batching 1;
2) get white clouds master slice 34g, 30 order gac 40g, 30 order zeolite 530g mixing and stirring, make batching 2;
3) finally step 1 and step 2 are made to batching and mix, mix on limit, and limit drips 4g phytic acid, makes the flocculation agent of 1000g.
Adopt appropriate this flocculation agent to process certain Chinese patent medicine factory influent COD, BOD is respectively the high density Chinese patent medicine waste water of 3200mg/L and 1650mg/L, after being disposed, the unified effluent quality of measuring, water outlet COD is 58.7mg/L, and BOD is 43.5mg/L, and clearance has reached respectively 98.2% and 97.4%.
Embodiment 3
1) get 1000 order ultra micro carapace powder particle 382g, modified chitosan 110g, nano titanium oxide 3g, stirs, and standing 2 hours, make the preliminary slaking of its character, make batching 1;
2) get white clouds master slice 21g, 30 order gac 20g, 30 order zeolite 460g mixing and stirring, make batching 2;
3) finally batching 1 and batching 2 are mixed, mix on limit, and limit drips 4g phytic acid, makes the flocculation agent of 1000g.Be applied to Chinese patent medicine waste water control.
Adopt appropriate this flocculation agent to process certain Chinese patent medicine factory influent COD, BOD is respectively the high density Chinese patent medicine waste water of 3200mg/L and 1650mg/L, after being disposed, the unified effluent quality of measuring, water outlet COD is 89.7mg/L, and BOD is 69.7mg/L, and clearance has reached respectively 97.2% and 95.8%.To contrasting before and after heavy metal, its every heavy metal content ratio on average declines 92% simultaneously, and major part is adsorbed in the mud that flocculation agent precipitates.
Embodiment 4
1) get 500 order ultra micro carapace powder particle 300g, modified chitosan 30g, nano titanium oxide 0.5g, stirs, and standing 2 hours, make the preliminary slaking of its character, make batching 1;
2) get white clouds master slice 10g, 30 order gac 10g, 30 order zeolite 550g mixing and stirring, make batching 2;
3) finally batching 1 and batching 2 are mixed, mix on limit, and limit drips 4g phytic acid, makes the flocculation agent of 1000g, is applied to Chinese patent medicine waste water control.
In laboratory, this flocculation agent specific aim is carried out to adsorption experiment to the heavy metal of Chinese patent medicine waste water, the in the situation that of enough flocculation agents, after processing, before and after heavy metal, contrast, its heavy metal total content ratio on average declines 94%.
Embodiment 5
1) get 800 order ultra micro carapace powder particle 300g, modified chitosan 120g, nano titanium oxide 5g, stirs, and standing 2 hours, make the preliminary slaking of its character, make batching 1;
2) get white clouds master slice 30g, 30 order gac 10g, 30 order zeolite 450g mixing and stirring, make batching 2;
3) finally batching 1 and batching 2 are mixed, mix on limit, and limit drips 4g phytic acid, makes the flocculation agent of 1000g, is applied to Chinese patent medicine waste water control.
By the flocculation agent of this proportioning, being applied to BOD is the BOD removal experiment of 1835mg/L Chinese patent medicine waste water, and 4g flocculation agent can be removed 1L and enter flocculation sediment and the follow-up BOD that 97.2% in waste water is provided.
Embodiment 6
1,800 order carapace powder particles: 40%
2, modified chitosan: 10%
3, nano titanium oxide: 0.5%
4, phytic acid: 0.5%
5, zeolite: 49%
Get 800 order ultra micro carapace powder particle 400g, modified chitosan 100g, nano titanium oxide 5g, stir, within static 2 hours, make its inner fully photochemical catalysis, sneak into afterwards 30 order zeolite powder 490g, mix and be added dropwise to phytic acid 5g while stirring, form finished product 1000g flocculation agent.This flocculation agent, can be applicable to process COD can be lower than 6000mg/L, BOD is lower than the improvement of the Chinese patent medicine waste water of 2500mg/L, every clearance is through practice, heavy metal removing rate can reach more than 95%, COD and BOD, through the processing of flocculation agent and the collaborative process of follow-up common process, can reach more than 95% clearance.。
Claims (7)
1. for a flocculation agent for Chinese patent medicine manufacturing enterprise waste water control, it is characterized in that, comprise following component: 30-45% carapace powder particle, 3-12% modified chitosan, 0.05-0.5% nano titanium oxide, 0.1-0.5% phytic acid, 45-55% zeolite; Described modified chitosan is with Fe
3+for properties-correcting agent, add nano titanium oxide, and add Mg
2+, prepare chitosan complex flocculation agent; Carapace powder particle is 500-1000 order.
2. flocculation agent according to claim 1, is characterized in that also containing 1-5% white mica and 1-5% gac.
3. flocculation agent according to claim 1 and 2, is characterized in that, described flocculation agent is composed as follows: 40% 800 order carapace powder particles, 10% modified chitosan, 0.5% nano titanium oxide, 0.5% phytic acid, 49% zeolite.
4. a preparation method for flocculation agent described in claim 1, is characterized in that, method is as follows:
1) get 300-450g ultra micro carapace powder particle, modified chitosan 30g-120g, nano titanium oxide 0.5g-5g, stirs, and standingly makes the preliminary slaking of its character, makes batching 1;
2) get zeolite 450g-550g mixing and stirring, make batching 2;
3) finally batching 1 and batching 2 are mixed, mix on limit, and limit drips 1g-5g phytic acid, makes the flocculation agent of 1000g.
5. method according to claim 4, is characterized in that, described batching 2 also adds 1-5% white mica and 1-5% gac.
6. method according to claim 4, is characterized in that, described modified chitosan is with Fe
3+for properties-correcting agent, add nano titanium oxide, and add Mg
2+, prepare chitosan complex flocculation agent.
7. method according to claim 4, is characterized in that, described carapace powder particle is for utilizing superfine communication technique to carry out miniaturization to crust, and the granularity that makes crust is 500-1000 object granularity.
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| CN104176796B (en) * | 2014-09-05 | 2016-08-24 | 江苏商达水务有限公司 | A kind of dephosphorization flocculating purifying agent and preparation and application thereof |
| CN104176802B (en) * | 2014-09-05 | 2016-04-20 | 江苏商达水务有限公司 | Flocculating purifying agent of a kind of pre-treatment rural area eutrophy waste water and preparation method thereof |
| CN105903266B (en) * | 2014-11-14 | 2018-01-02 | 济南沃特佳环境技术股份有限公司 | Heavy metal in water and the nano combined filtrate that can be sterilized can be removed |
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| CN108079961A (en) * | 2016-11-22 | 2018-05-29 | 天津工业大学 | A kind of new adsorbent for heavy metal and preparation method thereof and purposes |
| CN106517464B (en) * | 2016-12-09 | 2019-05-03 | 南京工业大学 | A kind of polymerization titanium salt modification of chitosan flocculant, preparation method and application |
| CN106746365B (en) * | 2017-02-17 | 2022-12-23 | 孙田力 | Module photocatalysis biomembrane sewage treatment device |
| CN111333162A (en) * | 2020-03-26 | 2020-06-26 | 王禹 | Natural polymeric flocculant and preparation method thereof |
| CN114272902B (en) * | 2021-12-14 | 2023-12-15 | 江苏载彤新材料股份有限公司 | Composite material for removing metallic copper ions in acidic wastewater and preparation method and application thereof |
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Address after: 214000 Jiangsu city of Wuxi province Xishan economic and Technological Development Zone No. 2 Feng Wei Lu savera No. 1 107&108 Patentee after: Jiangsu Eic water Co., Ltd. Address before: 214000 Xishan Economic Development Zone, Wuxi, Furong Road No. 99, No., No. three Patentee before: Jiangsu Shangda Water Affair Co., Ltd. |