CN1111016C - Preparation method of detoxicated algae - Google Patents
Preparation method of detoxicated algae Download PDFInfo
- Publication number
- CN1111016C CN1111016C CN99116395A CN99116395A CN1111016C CN 1111016 C CN1111016 C CN 1111016C CN 99116395 A CN99116395 A CN 99116395A CN 99116395 A CN99116395 A CN 99116395A CN 1111016 C CN1111016 C CN 1111016C
- Authority
- CN
- China
- Prior art keywords
- detoxification
- algae
- water
- ozone
- drying
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 241000195493 Cryptophyta Species 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title abstract description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000001784 detoxification Methods 0.000 claims abstract description 44
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 5
- 239000004744 fabric Substances 0.000 claims abstract 2
- 238000000643 oven drying Methods 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 13
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000003053 toxin Substances 0.000 abstract description 25
- 231100000765 toxin Toxicity 0.000 abstract description 25
- 108700012359 toxins Proteins 0.000 abstract description 25
- 231100000614 poison Toxicity 0.000 abstract 1
- 239000002574 poison Substances 0.000 abstract 1
- 238000011282 treatment Methods 0.000 description 16
- 230000000694 effects Effects 0.000 description 10
- 238000001514 detection method Methods 0.000 description 9
- 210000004027 cell Anatomy 0.000 description 8
- 108010049746 Microcystins Proteins 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- SRUWWOSWHXIIIA-UKPGNTDSSA-N Cyanoginosin Chemical compound N1C(=O)[C@H](CCCN=C(N)N)NC(=O)[C@@H](C)[C@H](C(O)=O)NC(=O)[C@H](CC(C)C)NC(=O)[C@H](C)NC(=O)C(=C)N(C)C(=O)CC[C@H](C(O)=O)N(C)C(=O)[C@@H](C)[C@@H]1\C=C\C(\C)=C\[C@H](C)[C@@H](O)CC1=CC=CC=C1 SRUWWOSWHXIIIA-UKPGNTDSSA-N 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- 108010067094 microcystin Proteins 0.000 description 4
- 241000192542 Anabaena Species 0.000 description 3
- 241000192700 Cyanobacteria Species 0.000 description 3
- 238000002965 ELISA Methods 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 3
- 241000192710 Microcystis aeruginosa Species 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 241000282412 Homo Species 0.000 description 2
- 241000192701 Microcystis Species 0.000 description 2
- 241000192656 Nostoc Species 0.000 description 2
- 241000192497 Oscillatoria Species 0.000 description 2
- 230000001154 acute effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000012851 eutrophication Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000003306 harvesting Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 210000004185 liver Anatomy 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000007903 penetration ability Effects 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000820 toxicity test Toxicity 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 206010011732 Cyst Diseases 0.000 description 1
- 229920002444 Exopolysaccharide Polymers 0.000 description 1
- 206010019851 Hepatotoxicity Diseases 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- 150000008575 L-amino acids Chemical class 0.000 description 1
- 241000059630 Nodularia <Cyanobacteria> Species 0.000 description 1
- IXBQSRWSVIBXNC-HSKGSTCASA-N Nodularin Chemical compound C([C@H](OC)[C@@H](C)\C=C(/C)\C=C\[C@H]1[C@@H](C(=O)N[C@H](CCC(=O)N(C)C(=C\C)/C(=O)N[C@H]([C@H](C)C(=O)N[C@@H](CCCN=C(N)N)C(=O)N1)C(O)=O)C(O)=O)C)C1=CC=CC=C1 IXBQSRWSVIBXNC-HSKGSTCASA-N 0.000 description 1
- IXBQSRWSVIBXNC-UHFFFAOYSA-N Nodularin Natural products N1C(=O)C(CCCN=C(N)N)NC(=O)C(C)C(C(O)=O)NC(=O)C(=CC)N(C)C(=O)CCC(C(O)=O)NC(=O)C(C)C1C=CC(C)=CC(C)C(OC)CC1=CC=CC=C1 IXBQSRWSVIBXNC-UHFFFAOYSA-N 0.000 description 1
- 208000012868 Overgrowth Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- 239000003619 algicide Substances 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 238000010171 animal model Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- JIGDOBKZMULDHS-UHFFFAOYSA-N cyanogenosin-RR Natural products N1C(=O)C(CCCN=C(N)N)NC(=O)C(C)C(C(O)=O)NC(=O)C(CCCN=C(N)N)NC(=O)C(C)NC(=O)C(=C)N(C)C(=O)CCC(C(O)=O)NC(=O)C(C)C1C=CC(C)=CC(C)C(OC)CC1=CC=CC=C1 JIGDOBKZMULDHS-UHFFFAOYSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 208000031513 cyst Diseases 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001631 haemodialysis Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000000322 hemodialysis Effects 0.000 description 1
- 230000007686 hepatotoxicity Effects 0.000 description 1
- 231100000304 hepatotoxicity Toxicity 0.000 description 1
- 231100000784 hepatotoxin Toxicity 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000007928 intraperitoneal injection Substances 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- 201000007270 liver cancer Diseases 0.000 description 1
- 208000019423 liver disease Diseases 0.000 description 1
- 208000014018 liver neoplasm Diseases 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- JIGDOBKZMULDHS-UUHBQKJESA-N microcystin RR Chemical compound C([C@H](OC)[C@@H](C)\C=C(/C)\C=C\[C@H]1[C@@H](C(=O)N[C@H](CCC(=O)N(C)C(=C)C(=O)N[C@H](C)C(=O)N[C@@H](CCCN=C(N)N)C(=O)N[C@H]([C@H](C)C(=O)N[C@@H](CCCN=C(N)N)C(=O)N1)C(O)=O)C(O)=O)C)C1=CC=CC=C1 JIGDOBKZMULDHS-UUHBQKJESA-N 0.000 description 1
- DIDLWIPCWUSYPF-UHFFFAOYSA-N microcystin-LR Natural products COC(Cc1ccccc1)C(C)C=C(/C)C=CC2NC(=O)C(NC(CCCNC(=N)N)C(=O)O)NC(=O)C(C)C(NC(=O)C(NC(CC(C)C)C(=O)O)NC(=O)C(C)NC(=O)C(=C)N(C)C(=O)CCC(NC(=O)C2C)C(=O)O)C(=O)O DIDLWIPCWUSYPF-UHFFFAOYSA-N 0.000 description 1
- 238000011328 necessary treatment Methods 0.000 description 1
- 108010065793 nodularin Proteins 0.000 description 1
- 230000001151 other effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930000044 secondary metabolite Natural products 0.000 description 1
- 238000011896 sensitive detection Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- Y02A40/948—
Landscapes
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Water Treatment By Sorption (AREA)
Abstract
本发明公开了一种藻类毒素脱毒的制备方法，其步骤是：首先是将藻脱水干燥，用40-160目滤布捕捞、沥干水分摊开，晾干、晒干或烘干，含水量在10%以下；其次是粉碎，将干燥的藻块粉碎成细的小颗粒藻粉；再次是加水，加水比例为1/10-1/20；第四是脱毒，藻粉的臭氧脱毒采用1-3%高浓度臭氧水脱毒或通含臭氧的空气(O3含量20%)脱毒。本发明脱毒快，效率高，成本低，操作简单。
The invention discloses a preparation method for detoxifying algae toxins. The steps are as follows: firstly, dehydrating and drying the algae, catching them with a 40-160 mesh filter cloth, draining the water, spreading them out, drying them in the air, drying them in the sun or oven-drying, containing The amount of water is less than 10%; the second is crushing, which is to crush the dried algae into fine small particles of algae powder; the third is to add water, the ratio of water addition is 1/10-1/20; the fourth is detoxification, the ozone detoxification of algae powder The poison is detoxified by using 1-3% high-concentration ozone water or passing through ozone-containing air (O 3 content 20%). The invention has fast detoxification, high efficiency, low cost and simple operation.
Description
本发明属于一种藻类资源毒素脱毒的制备方法。The invention belongs to a preparation method for detoxification of algal resource toxins.
随着全球性的水体富营养化，水华的发生越来越严重。水华是由于水体富营养化导致藻类(最常见的是蓝藻)过度繁殖而在水面聚集的结果。现已发现，水华中的蓝藻能释放大量对水体、对环境造成污染的藻类毒素。藻类毒素对水体的污染给人类带来严重的问题。它对水体中的生物具有较大的毒性，不仅可能通过食物链，食物网使生态系统遭到严重破坏，生物多样性下降；更严重的是许多毒素化学结构较稳定，它能通过食物链给人体带来潜在的危害。蓝藻毒素主要有微囊藻、颤藻、念珠藻等产生的微囊藻毒素(Microcystin，MC，MCYST)；某些鱼腥藻产生的鱼腥藻毒素；泡沫节球藻产生的Nodularin肝毒素等。其中，分布最广泛、最常见、危害最大的是微藻囊藻毒素。With the global eutrophication of water bodies, the occurrence of algal blooms is becoming more and more serious. Algal blooms are the result of overgrowth of algae, most commonly cyanobacteria, that accumulate on the water surface due to eutrophication of the water body. It has been found that cyanobacteria in water blooms can release a large amount of algae toxins that pollute water bodies and the environment. The pollution of water bodies by algae toxins has brought serious problems to human beings. It is highly toxic to organisms in the water body, not only may pass through the food chain, but the food web will seriously damage the ecosystem and reduce biodiversity; what is more serious is that many toxins have relatively stable chemical structures, and they can bring to the human body through the food chain. to potential hazards. Cyanotoxins mainly include Microcystin (MC, MCYST) produced by Microcystis, Oscillatoria, Nostoc, etc.; Anabaena produced by some Anabaena; Nodularin hepatotoxin produced by Nodularia foam, etc. . Among them, the most widely distributed, the most common, and the most harmful is the microalgal cyst algae toxin.
微囊藻毒素是淡水水华的主要成分蓝藻的次生代谢产物，是极强烈的肝癌促进剂。现已证明，微囊藻毒素很可能广泛存在于全世界富营养化的水体中。微囊藻毒素存在于蓝藻的微囊藻属(Microcystis)、鱼腥藻属(Anabaena)、颤藻属(Oscillatoria)及念珠藻属(Nostoc)某些种或品系的细胞中，它是一种环状多肽，通常结构为：环(D-丙氨酸-L-X-赤-β-甲基-D-异天冬氨酸-L-Y-Adda-D-异谷氨酸-N-甲基脱氢丙氨酸)。其中，Adda为一种特殊的氨基酸，结构为：3-氨基-9-甲氧基-2，6，8-三甲基-10-苯-癸-4，6-二烯酸。X，Y为两种可变的L氨基酸。因其不同可产生50多种微囊藻毒素。其中，含量较多的是MC-RR、MC-LR和MC-YR。微囊藻毒素的毒性作用最常见的表现是引起急性肝中毒。大量的实验证明，无论腹腔注射还是口服，都能在1-4小时内使实验动物肝脏严重损伤及至死亡。目前国内已有大量在水华严重的地区肝病 发生率上升的报道。国外也有因血液透析用水被微囊藻毒素污染而导致大批病人急性肝中毒死亡的报道。由于藻类毒素特别是微囊藻毒素对环境的污染，给人类带来的潜在威胁，以及在利用水华生物量方面成为重要障碍。近几年的国内外的研究多集中于毒素的发生机理、对生物体的危害、在生物体内及自然界中的降解等方面，如何除去藻类毒素的工作则做得相对较少。多种藻类毒素的分子结构稳定，很难分解，常规的方法如曝晒、加热、煮沸等去毒效果均不显著。国外对被藻毒素污染的水体的处理主要是以预防为主：当水体毒素浓度较低时，用活性炭处理，使用杀藻剂，监控水质维持继续供水；当毒素浓度升高时，只能紧急停水供水改变水源。经检索，在国内外尚未找到有关对藻毒素进行有效脱毒的报道。Microcystin is a secondary metabolite of cyanobacteria, the main component of freshwater blooms, and is a very strong promoter of liver cancer. It has been shown that microcystins are likely to be widespread in eutrophic water bodies worldwide. Microcystin exists in the cells of certain species or strains of cyanobacteria Microcystis, Anabaena, Oscillatoria and Nostoc. Cyclic polypeptides, usually with the structure: ring (D-alanine-L-X-erythro-β-methyl-D-isoaspartic acid-L-Y-Adda-D-isoglutamic acid-N-methyl dehydrogenation alanine). Among them, Adda is a special amino acid with the structure: 3-amino-9-methoxy-2,6,8-trimethyl-10-benzene-decane-4,6-dienoic acid. X, Y are two variable L amino acids. Because of its different can produce more than 50 kinds of microcystins. Among them, MC-RR, MC-LR and MC-YR are the most abundant. The most common manifestation of the toxic effects of microcystins is acute hepatotoxicity. A large number of experiments have proved that no matter intraperitoneal injection or oral administration, it can seriously damage the liver of experimental animals and even die within 1-4 hours. At present, there have been a large number of reports on the increase in the incidence of liver disease in areas with severe algae blooms in China. There are also reports abroad that a large number of patients died of acute liver poisoning due to the pollution of microcystin in hemodialysis water. Due to the pollution of the environment by algal toxins, especially microcystins, the potential threat to humans has become an important obstacle in the utilization of algae bloom biomass. In recent years, research at home and abroad has mostly focused on the mechanism of toxins, harm to organisms, and degradation in organisms and in nature. Relatively little work has been done on how to remove algae toxins. The molecular structure of various algae toxins is stable and difficult to decompose. Conventional methods such as exposure, heating, boiling, etc. have no significant detoxification effect. The treatment of water bodies polluted by algae toxins in foreign countries is mainly based on prevention: when the concentration of toxins in the water is low, treat with activated carbon, use algicides, monitor the water quality and maintain water supply; when the concentration of toxins rises, only emergency Cut off the water supply and change the water source. After retrieval, no reports about effective detoxification of algae toxins have been found at home and abroad.
本发明的目的是提供了一种藻类脱毒的方法，在藻类处理过程中加入臭氧，脱毒快，提高了脱毒效率。The purpose of the present invention is to provide a method for detoxification of algae, adding ozone in the process of algae treatment, so that the detoxification is fast and the detoxification efficiency is improved.
为了达到上述的目的，本发明采用了以下技术措施，其步骤是：In order to achieve the above-mentioned purpose, the present invention has adopted following technical measure, and its steps are:
A、由于臭氧具有极强的氧化能力，它不仅仅与毒素分子发生作用，还与处理样品中的大量其它物质反应，降低臭氧的利用率。因此要对材料进行必要的处理。在对有毒藻类进行臭氧处理前，首先应将收获后的藻烘干或晒干以使其脱水干燥，含水量在10％以下，并用粉碎机粉碎成藻粉(颗粒平均小于0.5mm)。A. Because ozone has a strong oxidizing ability, it not only reacts with toxin molecules, but also reacts with a large number of other substances in the processed sample, reducing the utilization rate of ozone. Therefore, the necessary treatment of the material should be carried out. Before the ozone treatment of toxic algae, the harvested algae should first be dried or sun-dried to make it dehydrated and dry, with a water content below 10%, and pulverized into algae powder (average particle size less than 0.5mm) with a pulverizer.
B、加入臭氧，臭氧处理的时间直接影响到脱毒的效果。臭氧处理时间过长，不仅造成浪费，且因副产物的增加而产生其它的效果。而处理时间过短，也会因反应不充分而达不到脱毒的效果。处理的时间应由含藻类毒素的量而定。用饱和臭氧水处理时间应控制在15-30分钟，通含臭氧的(O3含量20％左右)脱毒时反应时间应控制在30-50分钟。B. Adding ozone, the time of ozone treatment directly affects the effect of detoxification. If the ozone treatment time is too long, it will not only cause waste, but also produce other effects due to the increase of by-products. If the treatment time is too short, the effect of detoxification will not be achieved due to insufficient reaction. The time of treatment should be determined by the amount of algae toxins contained. The treatment time with saturated ozone water should be controlled at 15-30 minutes, and the reaction time should be controlled at 30-50 minutes during detoxification with ozone-containing (O 3 content about 20%).
C、加水，在藻的处理过程加适量的水，使藻在水溶液中所占比例为5-10％。处理过程中藻与所加水的比例应在1/10-1/20。加水量直接影响到臭氧分子在藻细胞内的渗透能力，影响到脱毒效果。C. Add water, add appropriate amount of water in the process of algae treatment, so that the proportion of algae in the aqueous solution is 5-10%. The ratio of algae to added water during treatment should be 1/10-1/20. The amount of water added directly affects the penetration ability of ozone molecules in algae cells and affects the detoxification effect.
图1为一种藻类脱毒的方法工艺流程图。Fig. 1 is a process flow diagram of a method for algae detoxification.
下面结合附图对本发明作进一步详细描述，其步骤是：Below in conjunction with accompanying drawing, the present invention is described in further detail, and its steps are:
1、水华的采收、与脱水干燥：由于水华富营养化水体的水面上分散分布，可用40目-160目的滤布捕捞，收获后沥干水分摊开，晾干、晒干或烘干，藻的含水量在10％以下，在藻干燥的过程中，新鲜的藻类细胞大多数在细胞外有一层厚厚的胞外多糖壁，它保护着在藻类细胞抵抗外界恶劣的生境。实验证明，在用臭氧对新鲜藻样进行脱毒时，相当长的时间内鲜藻样品中MC含量保持稳定。对新鲜藻样进行处理，并在脱毒过程中使其回到水环境中吸水膨胀，可使其细胞壁和胞内各种生物膜发生破裂，为臭氧顺利进入细胞内与毒素分子反应提供了方便，从而大大提高了脱毒效果。保持通风，缩短干燥时间，防止藻样发酵腐败。1. Harvesting, dehydration and drying of water blooms: due to the scattered distribution of water blooms on the surface of eutrophic water bodies, they can be caught with filter cloths of 40 mesh to 160 mesh. After harvesting, drain the water and spread out, dry, sun dry or bake Drying, the water content of the algae is below 10%. During the drying process of the algae, most of the fresh algae cells have a thick exopolysaccharide wall outside the cells, which protects the algae cells against the harsh environment of the outside world. Experiments have proved that when ozone is used to detoxify fresh algae samples, the MC content in fresh algae samples remains stable for a long time. Treat fresh algae samples and make them return to the water environment to absorb water and swell during the detoxification process, which can rupture the cell walls and various biofilms in the cells, and provide convenience for ozone to enter the cells and react with toxin molecules , thereby greatly improving the detoxification effect. Keep ventilation, shorten the drying time, and prevent algal fermentation from spoilage.
2、粉碎：将上述干燥的藻类通过粉碎机粉碎，使干燥的藻块粉碎成细的小颗粒藻粉(颗粒应小于0.5mm)。以有利于下一步脱毒过程中臭氧在藻细胞内的渗透，提高臭氧的利用率，提高脱毒的效果。2. Pulverization: the above-mentioned dried algae are pulverized by a pulverizer, so that the dried algae blocks are pulverized into fine small particles of algae powder (particles should be less than 0.5mm). In order to facilitate the penetration of ozone in algae cells in the next detoxification process, improve the utilization rate of ozone and improve the effect of detoxification.
3、藻粉的脱毒：有脱毒过程中在水环境中进行，臭氧分子是存在水环境下才能有效地通过生物膜与毒素反应，达到脱毒的效果，藻粉的臭氧脱毒可采取高浓度臭氧水脱毒或通含臭氧的空气(O3含量20％左右)脱毒。3. Detoxification of algae powder: In the process of detoxification, it is carried out in the water environment. Only in the presence of water environment can ozone molecules effectively pass through the biofilm and toxin reaction to achieve the effect of detoxification. The ozone detoxification of algae powder can be taken High-concentration ozone water detoxification or ozone-containing air (O 3 content about 20%) detoxification.
A、在脱毒池中加入1-3％的高浓度臭氧水(容器体积的2/5-3/5左右)，再按重量/体积比为1/10-1/20加入经过粉碎后的藻粉，搅拌后封闭处理池反应15-30分钟。处理池内的压力，不超过1.5个大气压，当压力过大时应打开减压阀减压(应将排出的气体通入臭氧吸收装置中。)反应完全后捞出藻，对之进行残留毒性的抽样检验。附高浓度臭氧水的制备：适量的净水(自来水即可)，通入含臭氧的空气使臭氧在水溶液中达到饱和，既得到高浓度臭氧水。A. Add 1-3% high-concentration ozone water (about 2/5-3/5 of the volume of the container) in the detoxification pool, and then add the pulverized water according to the weight/volume ratio of 1/10-1/20 Algae powder, after stirring, close the treatment pool and react for 15-30 minutes. The pressure in the treatment pool should not exceed 1.5 atmospheres. When the pressure is too high, the pressure relief valve should be opened to reduce pressure (the exhausted gas should be passed into the ozone absorption device.) After the reaction is complete, the algae should be fished out and tested for residual toxicity. Sampling inspection. Preparation of high-concentration ozone water: Appropriate amount of clean water (tap water is enough), pass through ozone-containing air to make the ozone saturated in the aqueous solution, and obtain high-concentration ozone water.
B、在脱毒处理池中加与A步骤等体积的水和经过粉碎后的藻粉(重量/体积比为同上)充分搅拌后封闭处理池，打开臭氧发生器反应30-50分钟，控制反应池内的压力(不超过1.5个大气压)，反应完全后捞出藻进行残留毒性的抽样检测。臭氧处理的浓度：臭氧脱毒是剧烈的氧化-还原反应，臭氧的浓度必须达到一定值。常用的卧管式臭氧发生器产生的臭氧浓度仅在1-3％左右，达不到预期的脱毒效果。水电解式臭氧发生器产生的臭氧浓度高，可达到脱毒的目的。B. Add the same volume of water as in step A and the pulverized algae powder (weight/volume ratio is the same as above) in the detoxification treatment tank, fully stir and then close the treatment tank, turn on the ozone generator to react for 30-50 minutes, and control the reaction The pressure in the pool (not more than 1.5 atmospheric pressure), after the reaction is complete, the algae are fished out for sampling detection of residual toxicity. Concentration of ozone treatment: Ozone detoxification is a violent oxidation-reduction reaction, and the concentration of ozone must reach a certain value. The ozone concentration produced by the commonly used horizontal tube ozone generator is only about 1-3%, which cannot achieve the expected detoxification effect. The ozone concentration produced by the water electrolytic ozone generator is high, which can achieve the purpose of detoxification.
4、毒素含量检测：由于藻类毒素的稳定性，即使低浓度的藻类毒素也可能通过食物链对人体产生毒害，因此必须对处理后物料的残余毒素进行检测。我们以对最常见、危害最大、分布最广泛的微囊藻毒素浓度的检测作为脱毒效果的指标。常用的检测方法有TLC检测法，LC/MS、酶联免疫吸附法(ELISA)、小白鼠毒性实验和HPLC检测法，可根据条件选择合适的检测方法。对严格控制毒素浓度的领域如医用品、化妆品领域毒素检测应以采用灵敏度高的检测方法如酶联免疫法和HPLC检测法测不出MC的存在为标准；一般性领域如饲料领域的MC含量可控制在10mg/千克干燥以下，采用小白鼠毒性实验即可。4. Detection of toxin content: Due to the stability of algae toxins, even low concentrations of algae toxins may cause poisoning to humans through the food chain, so residual toxins in processed materials must be detected. We use the detection of the concentration of the most common, most harmful, and most widely distributed microcystins as an indicator of the detoxification effect. Commonly used detection methods include TLC detection method, LC/MS, enzyme-linked immunosorbent assay (ELISA), mouse toxicity test and HPLC detection method, and the appropriate detection method can be selected according to the conditions. For fields that strictly control the concentration of toxins, such as medical supplies and cosmetics, the detection of toxins should be based on the use of highly sensitive detection methods such as enzyme-linked immunoassays and HPLC detection methods that cannot detect the presence of MC; It can be controlled below 10mg/kg dry, and the mouse toxicity test can be used.
本发明与现有技术相比，具有以下优点或效果：Compared with the prior art, the present invention has the following advantages or effects:
1、安全性高、无须后处理：臭氧在脱毒过程中分解成对人体、对环境无害的氧气，不会因脱毒剂过量而造成二次污染。臭氧的半衰期短，20℃时1％的臭氧水中臭氧衰变成氧气的半衰期仅为16分钟。1. High safety and no need for post-treatment: Ozone is decomposed into oxygen that is harmless to the human body and the environment during the detoxification process, and will not cause secondary pollution due to excessive detoxification agents. The half-life of ozone is short, and the half-life of ozone decaying into oxygen in 1% ozone water at 20°C is only 16 minutes.
2、脱毒过程短，效率高：臭氧是一种极强的氧化剂，它能迅速2. The detoxification process is short and efficient: ozone is a very strong oxidant, it can quickly
作用于毒素分子将其降解而达到彻底脱毒的目的。臭氧的氧化能力是氯的两倍，杀菌能力是氯的数百倍。由于臭氧具有极强的氧化能力和扩散渗透能力，用它进行脱毒，大大缩短了脱毒进程，提高脱毒效率。Act on toxin molecules to degrade them to achieve the purpose of complete detoxification. The oxidizing ability of ozone is twice that of chlorine, and the bactericidal ability is hundreds of times that of chlorine. Because ozone has a strong oxidation ability and diffusion and penetration ability, using it for detoxification can greatly shorten the detoxification process and improve the detoxification efficiency.
3、成本低、投资少、操作简单、易于维护。3. Low cost, less investment, simple operation and easy maintenance.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99116395A CN1111016C (en) | 1999-03-24 | 1999-03-24 | Preparation method of detoxicated algae |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99116395A CN1111016C (en) | 1999-03-24 | 1999-03-24 | Preparation method of detoxicated algae |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1268317A CN1268317A (en) | 2000-10-04 |
| CN1111016C true CN1111016C (en) | 2003-06-11 |
Family
ID=5279218
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99116395A Expired - Fee Related CN1111016C (en) | 1999-03-24 | 1999-03-24 | Preparation method of detoxicated algae |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1111016C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107410836A (en) * | 2017-04-07 | 2017-12-01 | 淮阴师范学院 | A kind of fruit juice clavacin ozone detoxification device and method |
| CN107279491A (en) * | 2017-08-09 | 2017-10-24 | 江苏纳克生物工程有限公司 | A kind of method of Microcystis aeruginosa fodder |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2093173U (en) * | 1991-05-04 | 1992-01-15 | 谢鲜武 | Advanced Health Drinking Water Preparer |
| CN2280090Y (en) * | 1996-12-21 | 1998-04-29 | 中国科学院广州能源研究所 | Photo-catalytic type water treatment equipment |
-
1999
- 1999-03-24 CN CN99116395A patent/CN1111016C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2093173U (en) * | 1991-05-04 | 1992-01-15 | 谢鲜武 | Advanced Health Drinking Water Preparer |
| CN2280090Y (en) * | 1996-12-21 | 1998-04-29 | 中国科学院广州能源研究所 | Photo-catalytic type water treatment equipment |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1268317A (en) | 2000-10-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Schmelling et al. | Photocatalytic transformation and mineralization of 2, 4, 6-trinitrotoluene (TNT) in TiO2 slurries | |
| Zhao et al. | Rational design of a bismuth oxyiodide (Bi/BiO1-xI) catalyst for synergistic photothermal and photocatalytic inactivation of pathogenic bacteria in water | |
| Chang et al. | The formation of disinfection by-products in water treated with chlorine dioxide | |
| Sreeja et al. | Photocatalytic water disinfection under solar irradiation by Ag@ TiO2 core-shell structured nanoparticles | |
| Assad et al. | Photo-catalytic and biological applications of phyto-functionalized zinc oxide nanoparticles synthesized using a polar extract of Equisetum diffusum D | |
| CN105854823B (en) | A kind of biological composite antibacterial adsorbent material and preparation method thereof | |
| Brillas et al. | Removal of paracetamol (acetaminophen) by photocatalysis and photoelectrocatalysis. A critical review | |
| Kaushal et al. | Metal organic framework-derived Zr/Cu bimetallic photocatalyst for the degradation of tetracycline and organic dyes | |
| Kannan et al. | Removal of plant poisoning dyes by adsorption on tomato plant root and green carbon from aqueous solution and its recovery | |
| CN105060389B (en) | A kind of method of perfluoro caprylic acid in precious metal doping gallium oxide photocatalytic degradation water | |
| Yan et al. | Effective removal of microcystins using carbon nanotubes embedded with bacteria | |
| Abilarasu et al. | Enhanced photocatalytic degradation of diclofenac by Sn0. 15Mn0. 85Fe2O4 catalyst under solar light | |
| Li et al. | The extent of sludge solubilization allows to estimate the efficacy of ozonation for removal of polycyclic aromatic hydrocarbons (PAHs) in municipal sewage sludge | |
| Jun et al. | Radiolysis of pentachlorophenol (PCP) in aqueous solution by gamma radiation | |
| Jiang et al. | Degradation and detoxification of neonicotinoid insecticides by a porous oxygen vacancy-rich BiOCl self-recovery system: Active site transfer enhances oxygen vacancies stability | |
| Liu et al. | Investigation of the photoelectric properties of nanostructured CeO2/Cu2O heterojunction: Photocatalytic degradation of sulfadiazine in water | |
| CN106219666A (en) | A method for Pt-doped In2O3 photocatalytic degradation of PFOA in water | |
| Cao et al. | 3D flower sphere Bi2S3/Bi4O5Br2 heterojunction: Alleviating photocorrosion and enhanced photocatalytic performance | |
| Zhou et al. | Construction of a BiOI/ZnO heterojunction on biomass Juncus effusus fiber for photodegradation of organic pollutants | |
| CN1111016C (en) | Preparation method of detoxicated algae | |
| Sarvani et al. | Adsorption isotherm and kinetics study: removal of phenol using adsorption onto modified pistacia mutica shells | |
| Mohsin et al. | Solar light driven degradation of piroxicam and paracetamol by heterogeneous photocatalytic fenton system: process optimization, mechanistic studies and toxicity assessment | |
| Nugroho et al. | Photocatalytic performance with electrochemical effects for ZnO/Graphene Quantum Dots/CdSe nanocomposite toward ciprofloxacin antibiotics and paracetamol degradation under visible light | |
| CN206121399U (en) | An organic waste gas purifier | |
| CN104162410A (en) | Preparation method of natural material adsorbent, and sewage treatment processing adopting natural material adsorbent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |