CN101578984A - Algaecide combined by cinnamic aldehyde, eugenol and citric acid - Google Patents
Algaecide combined by cinnamic aldehyde, eugenol and citric acid Download PDFInfo
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- CN101578984A CN101578984A CNA2009100097970A CN200910009797A CN101578984A CN 101578984 A CN101578984 A CN 101578984A CN A2009100097970 A CNA2009100097970 A CN A2009100097970A CN 200910009797 A CN200910009797 A CN 200910009797A CN 101578984 A CN101578984 A CN 101578984A
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Abstract
The invention discloses an algaecide. The algaecide mainly comprises cinnamic aldehyde, eugenol and citric acid, wherein the content of the cinnamic aldehyde is between 0.01 and 5.0ml/l; the content of the eugenol is between 0.01 and 5.0ml/l; the mass content of the citric acid is between 1.0 and 5.0 percent; the content of azone is between 1.0 and 1.5 percent; and the content of NP-10 is between 8 and 15 percent. The algaecide has good algae-killing effect, wide range of pH application and convenient and safe use, cannot cause secondary pollution to the environment, has deodorizing effect, and can be widely applied to algae-killing and water purifying treatment for natural and landscape water bodies.
Description
Technical field
The invention belongs to the environmental protection field, specifically relate to a kind of cinnamic acid, eugenol and citric acid of containing, be used for the removal preparation of nature, landscape water body and water for industrial use algae.
Background technology
Algicide is a class water treatment agent commonly used.Body eutrophication causes algae excessive propagation in the water and forms " wawter bloom ", reduces water transparency, and oxygen in water is sharply descended, and causes aquatile mortalities such as fish, even harm humans health.Landscape water body and water for industrial use also are subjected to many influences because of a large amount of breedings of algae, bring the tremendous economic loss.At present, the removal method of algae mainly is divided into physics method, chemical method and bioanalysis.Chemical method is used widely because of it kills advantages such as algae efficient height, price be low, easy to use.
The common chemical algicide mainly divides two big classes according to killing algae mechanism: oxidized form algicide and flocculation type algicide.Oxidized form kill the algae product can the oxidizing microorganisms body in metabolic closely-related enzyme, cause microbial metabolism disorderly so that dead.Yet this class algicide contains halides more, and the water body organism of energy halogenation often produces carcinogenic product, danger side of body human health.The flocculation type kills the algae product and mostly is the metal species salting liquid, and on the one hand the eubolism that suppresses algae by metal ion disturbs algae grows, and then the flocculation sedimentation algae by metal ion reaches purpose except that algae on the other hand.Yet the algae product that removes that these get instant result has all brought secondary pollution to environment inevitably when removing algae, as heavy metal pollution and haloform pollution etc.
Therefore, need that screening is new and effective, the compound of low toxicity and develop environmentally friendly, to the novel environment friendly algicide of people's safety.
Summary of the invention
In order to overcome present chemical classes algicide to the secondary pollution problem that environment brings, the invention provides a kind of new and effective, safe in utilization, environment amenable environmental-protecting chemical algicide.
1, the composition of algicide and preparation
But active ingredient of the present invention is the Secondary Metabolism of Plant product of synthetic, comprises cinnamic acid, eugenol and citric acid.
Cinnamic acid eugenol citric acid
Cinnamic acid (Cinnamaldehyde), chemical name are 3-phenyl-2-acrolein, and proterties is colourless or weak yellow liquid, and the fragrance of cassia oil and cinnamon oil is arranged.Boiling point is 248 ℃, and fusing point is-8 ℃, and is water-soluble slightly, is dissolved in ethanol and the ether, is insoluble in the benzinum.Can volatilize with steam.Rat oral toxicity LD50 is 2.22g/kg.Aspect medical, has sterilizing corrosion-resistant effect, to Escherichia coli, hay bacillus and staphylococcus aureus, staphylococcus albus, Shigella shigae, typhoid fever and paratyphoid A bacillus, pneumococcus, aerobacteria, proteus, bacillus anthracis, Bacterium enteritidis, comma bacillus etc. have inhibitory action.And remarkable to the gram-positive bacteria bactericidal effect, can be used for treating the multiple disease that causes because of bacterial infection.In the food flavor industry, cinnamic acid is become food additives by the U.S. and Japan's exploitation because of its sterilization, sterilization and corrosion-resistant function, and it is as food preservative, and the nontoxic or low toxicity to human body also can play stronger inhibitory action to the breeding of microorganism.Because cinnamic acid all has stronger disinfection function for acid or alkaline material, can be widely used in anticorrosion anti-mildew fresh-keeping.Because of cinnamic acid not only safety and environmental protection but also smell fragrance, at chemical field, be developed to multiple antimicrobial, can be used for insecticide, culicifuge, air freshener, antistaling agent, refrigerator deodorizer etc., cinnamic acid also can be used for Biocidal algae-killing agent, the turbid rotten agent of acidifying in the oil exploitation etc.
Eugenol (Eugenol), chemical name are 2-methoxyl group-4-acrylic-phenol, and proterties is colourless or pale yellow liquid.Boiling point is 255 ℃, and fusing point is-9.2 ℃, and is water-soluble hardly, with ethanol, chlorine, ether and oil can be miscible.Rat oral toxicity LD50 is 1.93g/kg.Have antibiotic, anti-inflammatory, effect such as antiviral, when 1: 8000～1: 16000 concentration, pathogenic fungus is had inhibitory action; When 1: 2000～1: 8000 concentration, bacillus such as staphylococcus aureus and pneumonia, dysentery, large intestine, distortion, tuberculosis all there is inhibitory action.
Citric acid (Citric acid), proterties are colourless translucent crystal or white crystalline powder, the extremely acid of odorless, flavor.Fusing point is 153 ℃ (dehydrations), decomposes more than 175 ℃ and emits water and carbonic acid gas.Soluble in water, ethanol and ether are insoluble to benzene, are slightly soluble in chloroform.Rat oral toxicity LD50 is 6.73g/kg.Be mainly used in spices or,, also be chemical intermediate at food with medically as sequestering agent as the acidulant of beverage.
The prescription that the present invention adopts is as follows:
Cinnamic acid: 0.01mL/L～5.0mL/L
Eugenol: 0.01mL/L～5.0mL/L
Citric acid: 1.0%～5.0%
Azone: 1.0%～1.5%
NP-10：8％～15％
The pH value that algicide of the present invention uses is≤10.0.
2, algae killing effect assay method
(1) algal control circle test
Employing contains the algistatic activity that the double-deck soft agar flat band method of algae is measured algicide of the present invention.Concrete grammar is: prepare 1% aqueous agar solution, evenly be laid in the culture dish after dissolving with microwave, be bottom platform after the condensation, to concentrate algae liquid and 50 ℃ 1% dissolve the agar solution equal proportion and mix on the bottom-layer agar that is poured into condensation and be upper panel, treat that top-layer agar also promptly gets after the condensation and contain algae bilayer soft agar flat board.Symmetry is placed the Oxford cup on this flat board, adds algicide to be measured and contrast medicament in the cup hole, and 25 ℃ of constant temperature illumination cultivation 48h take down the Oxford cup in the illumination box, measure the algal control loop diameter, analyze algae killing effect.
(2) chlorophyll α changes and transparency analysis
Remove the algae effect that purifies water by what (Chl-α) assay of chlorophyll α in the water sample and water transparency were observed checking algicide of the present invention.Concrete grammar is: algicide of the present invention is added in pending water sample or the water body in 1%～10% ratio (deciding on the algal grown situation in the water sample), leave standstill behind the mixing, sampling 90% methyl alcohol is handled 10min for 60 ℃ after handling 24h, get supernatant after centrifugal, the absorbance value of its 665nm of spectrophotometric determination, 645nm and 635nm, by formula Chl-α (mg/L)=11.6A
665-1.31A
645-0.14A
635Calculate the content of chlorophyll α, observe water sample or water transparency simultaneously.
(3) algae quantitative changeization and microscopic observation
In the absorbance value situation of change at 600nm place, verify the removal effect of algicide of the present invention by microexamination counting statistics and algae liquid to frustule in the water body.
The mechanism of action of algicide of the present invention is: destroy frond structure and organelle, suppress algae photosynthesis.Algicide of the present invention also has killing livestock property of wide spectrum, promptly multiple microorganism is had stronger killing and the inhibition ability, and the speed of killing livestock is fast, the power of killing livestock is strong, applicable pH value wide ranges, general pH value≤10.0 all can be suitable for, even still have advantages of higher stability under alkali condition.In addition, each component of algicide of the present invention (cinnamic acid, eugenol and citric acid) toxicity is little, and has been widely used in food processing and fragrance industry as food additives and spices, to people, animal safety, environment is also had no adverse effects, and has deodorizing effect simultaneously concurrently.
Algicide proterties of the present invention is stable, but long term storage is the reliable molten algae bactericide of a kind of ideal in the shady and cool ventilation place.
Description of drawings
The present invention is further described below in conjunction with drawings and Examples.
Fig. 1 contains the algistatic activity figure that the double-deck soft agar flat band method of algae is measured algicide of the present invention.
Fig. 2 is the transparency interaction figure after algicide of the present invention is handled the microcystic aeruginosa 24h of artificial culture.
Fig. 3 is that algicide of the present invention is handled chlorophyll alpha content figure behind the microcystic aeruginosa 24h of artificial culture.
Fig. 4 is the transparency interaction figure after algicide of the present invention is handled Taihu Lake wawter bloom algae sample 48h.
Fig. 5 is the frustule morphology displaing micro picture of Taihu Lake wawter bloom algae sample after algicide of the present invention is handled 48h.
Fig. 6 is an algae quantitative change situation map during the field trial of gate of a village estuary waters, Taihu Lake, Wuxi.
Embodiment
With the algicide of cinnamic acid, eugenol and citric acid preparation, be called for short the fragrant sour algicide in osmanthus, be numbered JSCD.Occur with the numbering form in following examples.
Embodiment one
Adopt the algistatic activity of algal control circle verification experimental verification JSCD, in the Oxford cup that symmetry is placed, add distilled water (negative control), 1mg/L CuSO respectively
4Each 200 μ L of solution (positive control) and 1%JSCD solution, measure the algal control loop diameter behind the illumination cultivation 48h, effect of algae restraint as shown in Figure 1, the negative contrast of A, B are that JSCD handles among Fig. 1, the algal control loop diameter is 35mm, and molten algae effect is significantly better than the CuSO shown in Fig. 1 C
4Handle (the algal control loop diameter is 25mm).
Embodiment two
Algicide JSCD of the present invention is added in 1% ratio in the microcystic aeruginosa liquid of artificial culture, continue to cultivate 24h, observe the content of handling back algae liquid transparency and measuring chlorophyll α.Fig. 2 is the transparency interaction figure of JSCD after handling, and Fig. 3 is the chlorophyll alpha content figure of JSCD after handling, and the diagram result shows that handling back algae liquid through JSCD becomes and clarify, and the chlorophyll alpha content significantly descends, and frustule is grown and is subjected to remarkable inhibition.The blank that ck sets up for test among the figure.
Embodiment three
Gather gate of a village Jiangkou, Taihu Lake, Wuxi blue-green algae between the month in 8-9 and salvage the fresh blue-green algae water sample of point, handle by 2% consumption with JSCD, observe algae killing effect after leaving standstill 48h through concentrating the back, and the microscope inspection observation frustule morphological change of taking a sample.As shown in Figure 4, handle the transparent clarification that becomes of back Taihu Lake wawter bloom algae water sample through JSCD, most of frond sinks, and microscopic examination shows that frustule breaks after the JSCD processing, the cell badly broken, and majority lies in fragments, shown in Fig. 5 B.
Embodiment four
On August 17th, 2008 was carried out the regional algae field trial of killing to August 21 at gate of a village Jiangkou, Taihu Lake, Wuxi.Experimental observation JSCD algae killing effect and hold time, mainly monitored add JSCD after, the situation of change of algae amount in the water.Specific implementation method is: the enclosure of each 2m of length and width is set, the about 1m of the depth of water, water volume 4m in one section serious waters of blue-green algae at gate of a village Jiangkou, Taihu Lake
3, in this enclosure, add JSCD and control the algae test.Divide 2 dosings, add by water volume 5% consumption at every turn, administration timing of drug is August 17 and August 19.As shown in Figure 6, after adding JSCD for the first time, the algae amount is by 1.34 * 10 in the 6h
5Individual/mL drops to 3.82 * 10
4Individual/mL, the 2nd day, algae amount had rebound significantly again, add medicament after, the algae amount descends rapidly, the algae amount maintained 5.2 * 10 substantially in the 4th day to the 5th day
4Individual/mL, illustrate add the JSCD algicide after, controlled algae grows more stablely.Kill the algae rate and can keep 60%～80% higher level.Because the set waters of test water body box haul carries out return type rolling stream mode, dosing is after one day, because current cause the inside and outside water exchange of enclosure serious, new algae enters enclosure, cause the 2nd day algae amount to go up, add medicament after the algae amount controlled, kill the algae rate and reach more than 75%.Entire test is owing to exist water body exchange and outside algae constantly to enter, and adding dose may be slightly higher, and algae killing effect then may be on the low side.To water sample observations of taking a sample in dispensing waters, the plankton that survives is in a large number arranged always before and after the dispensing during the whole test, near the aquatiles such as fish in waters, testing ground also survive well.
Embodiment five
On August 23rd, 2008 is to August 25, in the Wuxi only fine jade farm simulate landscape water body kill the algae test.Test is carried out in the artificial cement pit of building in the ecological farm of fine jade only, the long 1.2m in pond, and the wide 0.8m in pond, the high 0.5m in pond, Yu Chizhong inject fresh Taihu Lake blue-green algae water sample, the about 0.3m of total amount volume
3, dosing takes once to add JSCD 2.5% consumption, and the pond contrast of being untreated is set up in test.After monitoring adds JSCD, the chlorophyll α in the water sample, algae content and kill the situation of change of algae rate.As shown in table 1, adding JSCD kills the algae rate and reaches more than 96% after 2 days.
Table 1 JSCD algicide Wuxi is the ecological demonstration of fine jade penalty kick algae test situation table only
Claims (4)
1, a kind of algicide is characterized in that, has following listed prescription by concentration and mass percent:
Cinnamic acid: 0.01mL/L～5.0mL/L
Eugenol: 0.01mL/L～5.0mL/L
Citric acid: 1.0%～5.0%
Azone: 1.0%～1.5%
NP-10：8％～15％
2, algicide according to claim 1 is characterized in that, the pH value scope that described algicide uses is≤10.0.
3, algicide according to claim 1 is characterized in that, the dosage of described algicide is 1%～5%, grows situation on the microorganism in the water and decides.
4, the described algicide of claim 1 is used killing in the algae processing of blue-green alga bloom waters and landscape water body.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100097970A CN101578984A (en) | 2009-01-22 | 2009-01-22 | Algaecide combined by cinnamic aldehyde, eugenol and citric acid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100097970A CN101578984A (en) | 2009-01-22 | 2009-01-22 | Algaecide combined by cinnamic aldehyde, eugenol and citric acid |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102415378A (en) * | 2011-11-30 | 2012-04-18 | 江苏省农业科学院 | Bactericide capable of promoting crop growth and preventing and treating pepper phytophthora blight, and use thereof |
| CN102422847A (en) * | 2011-10-18 | 2012-04-25 | 浙江农林大学 | Weed killer containing plant essential oil, and application thereof |
| CN102939965A (en) * | 2012-11-05 | 2013-02-27 | 温文 | Cinnamyl aldehyde algicide |
| CN103936121A (en) * | 2014-04-18 | 2014-07-23 | 芜湖凯奥尔环保科技有限公司 | Mosquito-repellent powder-like blue-green algae treatment agent and preparation method thereof |
| CN109896601A (en) * | 2019-03-06 | 2019-06-18 | 上海盛安消防工程有限公司 | A kind of fire demand water inorganic agent and its preparation process |
| CN112841214A (en) * | 2021-01-22 | 2021-05-28 | 济南天邦化工有限公司 | Plant source synergistic glufosinate-ammonium aqua and preparation method and application thereof |
| CN112889849A (en) * | 2021-01-26 | 2021-06-04 | 中国海洋大学 | Composite plant extracts, compositions and methods of use for controlling the growth of cladophora |
| WO2023045943A1 (en) * | 2021-09-27 | 2023-03-30 | 中国农业科学院都市农业研究所 | Alga inhibition material and application thereof in soilless culture |
-
2009
- 2009-01-22 CN CNA2009100097970A patent/CN101578984A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102422847A (en) * | 2011-10-18 | 2012-04-25 | 浙江农林大学 | Weed killer containing plant essential oil, and application thereof |
| CN102415378A (en) * | 2011-11-30 | 2012-04-18 | 江苏省农业科学院 | Bactericide capable of promoting crop growth and preventing and treating pepper phytophthora blight, and use thereof |
| CN102939965A (en) * | 2012-11-05 | 2013-02-27 | 温文 | Cinnamyl aldehyde algicide |
| CN103936121A (en) * | 2014-04-18 | 2014-07-23 | 芜湖凯奥尔环保科技有限公司 | Mosquito-repellent powder-like blue-green algae treatment agent and preparation method thereof |
| CN103936121B (en) * | 2014-04-18 | 2016-03-09 | 芜湖凯奥尔环保科技有限公司 | A kind of can the Powdered blue algae treatment agent and preparation method thereof of mosquito repellent |
| CN109896601A (en) * | 2019-03-06 | 2019-06-18 | 上海盛安消防工程有限公司 | A kind of fire demand water inorganic agent and its preparation process |
| CN112841214A (en) * | 2021-01-22 | 2021-05-28 | 济南天邦化工有限公司 | Plant source synergistic glufosinate-ammonium aqua and preparation method and application thereof |
| CN112889849A (en) * | 2021-01-26 | 2021-06-04 | 中国海洋大学 | Composite plant extracts, compositions and methods of use for controlling the growth of cladophora |
| CN112889849B (en) * | 2021-01-26 | 2022-01-04 | 中国海洋大学 | Composite plant extracts, compositions and methods of use for controlling the growth of cladophora |
| WO2023045943A1 (en) * | 2021-09-27 | 2023-03-30 | 中国农业科学院都市农业研究所 | Alga inhibition material and application thereof in soilless culture |
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Application publication date: 20091118 |