CN102887581A - 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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- CN102887581A CN102887581A CN2012104017727A CN201210401772A CN102887581A CN 102887581 A CN102887581 A CN 102887581A CN 2012104017727 A CN2012104017727 A CN 2012104017727A CN 201210401772 A CN201210401772 A CN 201210401772A CN 102887581 A CN102887581 A CN 102887581A
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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, specifically be applicable to the improvement of Chinese patent medicine manufacture sewage.
Background technology
The Chinese patent medicine that it has often been said in the life refers to be made by the principle prescription of necessarily curing the disease by Chinese medicinal materials, and the ready-made medicine that can take at any time is such as various pills, powder, electuary etc.Advantage be ready-made available, adapt to be badly in need of, storage makes things convenient for, can carry, saved the decoction decoction process, eliminated Chinese herbs decoction distinctive peculiar smell and pessimal stimulation etc. when 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, have organic contamination substrate concentration height, and suspension content is high, and colourity is high, the unsettled characteristics 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 wherein is unfavorable for biochemical treatment, can reduce cost of sewage disposal, and be conducive to the recycling of mud behind the flocculation sediment.
Its source of Chinese patent medicine sewage mainly is that equipment flushing, medicinal material clean, extract concentrated and the workshop flushing, and living facilities.Principal pollutant are natural organic matter, such as water miscible carbohydrate, glycoside, Anthraquinones, tannin, organic acid, xylogen, alkaloid, tannin, protein, starch, grease etc., the pollutent of non-solubility mainly comes self-stip, extracts silt, the plant suspended substance of workshop section, and also having some is some heavy metal substances that exist in the Chinese medicine.Facts have proved, some Chinese patent medicine factory effluent organic concentration is high, complicated component, and the characteristics 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, causes compatriots' concern always.
Chitosan is a kind of natural organic high-molecular compound, widely applies industrial as water conditioner, 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 the chitosan that wherein is used for water treatment reaches 500 tons more than every year.Itself has no side effect chitosan, fully biodegradable, its structure is the straight chain macromole, contain a plurality of hydroxyls, amino isoreactivity group on the molecule, the organism such as metal ion, dyestuff look ion, halogen, protein, amino acid and clay particle there is good chemisorption, tool bactericidal ability preferably also can be used to prepare the high-efficient low-toxicity multifunctional flocculation agent aspect water treatment simultaneously.
Chitosan (Chitosan, CHI) is a kind of natural polymers, can process decalcification, deproteinization and fat by shrimp and crab shells through diluted acid, diluted alkaline first and obtain similar in cellulosic chitin, and then deacetylate obtains in concentrated alkali solution.Chitosan is a kind of high performance heavy metal capturing agent, this mainly has benefited from the 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 good sequestering action, and it can remove the heavy metal ion such as copper in the 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, be a kind of natural macromolecule flocculating agent that good development prospect is arranged, Japan and other countries has been used for it the processing of urban domestic wastewater and trade effluent.
Summary of the invention
For existing problem in the Chinese patent medicine production, the invention provides a kind of efficient and manageable for the employed biological activity flocculation agent of 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 the 10-30 order.
Described carapace powder particle is the 500-1000 order, the environmental problem that can't recycle for solving the crust that exists in present many aquaculture field, we have selected the refuse shell is recycled especially, utilize superfine communication technique that crust is carried out miniaturization, studied the factor that affects crushing effect in crushing process, the factor of major control has: the time, feeding, the muller gap, wind-force etc., the granularity that makes the target crust is 500-1000 purpose granularity.
500-1000 purpose carapace powder particle, be applicable to the 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 its flocculation sediment in earlier stage and processes.
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 leaves standstill to make the preliminary slaking of its character, makes batching 1; Get zeolite 450g-550g mixing and stirring, make batching 2; To prepare burden at last 1 and batching 2 mix, mix on the limit, the limit drips the 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 the common pH(7 of waste water～9) flocculating effect is relatively poor when using separately under the condition, the present invention strengthens its stability and cationic properties by modification, improve it to the removal ability of the electronegativity particle in the water body, make it to keep to COD the efficient clearance of SS.
Described modified chitosan is with Fe
3+Be properties-correcting agent, add micro-nano titanium oxide, and add Mg
2+, having prepared the chitosan complex ferric flocculant, described modified chitosan optimal preparation technology is: at first chitosan is made the aqueous solution, then with Fe
3+Be properties-correcting agent and chitosan complex, make by the iron ion of complexing by adjusting acidity to be hydrolyzed in right amount again that nano titanium oxide is the 0.01-0.15% of 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.Tested the flocculating property of chitosan complex iron to waste water with standard method, shown when pH=7, flocculating effect (rate of descent) is 92.56%, and has and need not regulate waste water acidity, go out the characteristics 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 not be at present special sewage-treating agent for the 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 the Chinese patent medicine factory effluent.Because biological flocculant of the present invention can specific aim be processed the present 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 the Chinese patent medicine sewage, also can be along with the later stage filters, produce preferably effect, make sewage have more biodegradability.
2, biological activity flocculation agent of the present invention, introduce the crust after chitosan and the 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, and 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, such as copper etc.
3, sorbent material commonly used has gac, active coal, humic acids, polymeric adsorbent etc., and the present invention has added phytic acid on sorbent material basis commonly used, further improved adsorptive power.
Embodiment
Further set forth technical scheme of the present invention below in conjunction with embodiment, 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 leaves standstill 0.5 hour, makes the preliminary slaking of its character, makes batching 1;
2) get white clouds master slice 30g, 10 order gac 20g, 30 order zeolite 450g mixing and stirring are made batching 2;
3) at last step 1 and step 2 are made batching and mix, mix on the limit, and the limit drips the 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 the capacity flocculation agent, and in conjunction with conventional Air Exposure, the COD water outlet is 147.3mg/L, can reach the above COD clearance of 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 leaves standstill 1.5 hours, makes the preliminary slaking of its character, makes batching 1;
2) get white clouds master slice 34g, 30 order gac 40g, 30 order zeolite 530g mixing and stirring are made batching 2;
3) at last step 1 and step 2 are made batching and mix, mix on the limit, and the limit drips the 4g phytic acid, makes the flocculation agent of 1000g.
Adopt an amount of 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 leaves standstill 2 hours, makes the preliminary slaking of its character, makes batching 1;
2) get white clouds master slice 21g, 30 order gac 20g, 30 order zeolite 460g mixing and stirring are made batching 2;
3) will prepare burden at last 1 and batching 2 mix, mix on the limit, the limit drips the 4g phytic acid, makes the flocculation agent of 1000g.Be applied to the Chinese patent medicine waste water control.
Adopt an amount of 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 the heavy metal, its every heavy metal content ratio on average descends 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 leaves standstill 2 hours, makes the preliminary slaking of its character, makes batching 1;
2) get white clouds master slice 10g, 30 order gac 10g, 30 order zeolite 550g mixing and stirring are made batching 2;
3) will prepare burden at last 1 and batching 2 mix, mix on the limit, the limit drips the 4g phytic acid, makes the flocculation agent of 1000g, is applied to the Chinese patent medicine waste water control.
In the laboratory, this flocculation agent specific aim is carried out adsorption experiment to the heavy metal of Chinese patent medicine waste water, in the situation of capacity flocculation agent, after processing, contrast before and after the heavy metal, its heavy metal total content ratio on average descends 94%.
Embodiment 5
1) get 800 order ultra micro carapace powder particle 300g, modified chitosan 120g, nano titanium oxide 5g stirs, and leaves standstill 2 hours, makes the preliminary slaking of its character, makes batching 1;
2) get white clouds master slice 30g, 30 order gac 10g, 30 order zeolite 450g mixing and stirring are made batching 2;
3) will prepare burden at last 1 and batching 2 mix, mix on the limit, the limit drips the 4g phytic acid, makes the flocculation agent of 1000g, is applied to the Chinese patent medicine waste water control.
With the flocculation agent of this proportioning, being applied to BOD is the BOD removal experiment of 1835mg/L Chinese patent medicine waste water, and the 4g flocculation agent can be removed 1L and enter flocculation sediment and the follow-up BOD that 97.2% in the 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, made its inner fully photochemical catalysis, and sneaked into afterwards 30 order zeolite powder 490g in static 2 hours, mix while stirring being added dropwise to phytic acid 5g, form finished product 1000g flocculation agent.This flocculation agent, can be applicable to process COD and 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 can reach the clearance more than 95% through the processing of flocculation agent and the collaborative process of follow-up common process.。
Claims (9)
1. a flocculation agent that is used for the waste water control of Chinese patent medicine manufacturing enterprise is characterized in that, 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.
2. flocculation agent according to claim 1 is characterized in that, described modified chitosan is with Fe
3+Be properties-correcting agent, add nano titanium oxide, and add Mg
2+, prepare the chitosan complex flocculation agent.
3. flocculation agent according to claim 1 is characterized in that also containing 1-5% white mica and 1-5% gac.
4. flocculation agent according to claim 1 is characterized in that, the carapace powder particle is the 500-1000 order.
5. 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.
6. the preparation method of the described flocculation agent of 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 leaves standstill to make the preliminary slaking of its character, makes batching 1;
2) get zeolite 450g-550g mixing and stirring, make batching 2;
3) will prepare burden at last 1 and batching 2 mix, mix on the limit, the limit drips the 1g-5g phytic acid, makes the flocculation agent of 1000g.
7. method according to claim 6 is characterized in that, described batching 2 also adds 1-5% white mica and 1-5% gac.
8. method according to claim 6 is characterized in that, described modified chitosan is with Fe
3+Be properties-correcting agent, add nano titanium oxide, and add Mg
2+, prepare the chitosan complex flocculation agent.
9. method according to claim 6 is characterized in that, described carapace powder particle is for utilizing superfine communication technique that crust is carried out miniaturization, and the granularity that makes crust is 500-1000 purpose granularity.
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| CN105692848A (en) * | 2016-02-23 | 2016-06-22 | 李清源 | Natural ingredient farm sewage flocculant |
| CN105692961A (en) * | 2016-03-11 | 2016-06-22 | 刘畅子 | Method for treating fish tank water |
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| CN106517464A (en) * | 2016-12-09 | 2017-03-22 | 南京工业大学 | Polymerization titanium salt modified chitosan flocculating agent, and preparation method and application thereof |
| 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 |
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