JP2008214600A - Heavy metal disposal material and soil improvement agent to reduce and remove heavy metal and food waste water, and heavy metal removal method - Google Patents

Heavy metal disposal material and soil improvement agent to reduce and remove heavy metal and food waste water, and heavy metal removal method Download PDF

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JP2008214600A
JP2008214600A JP2007096831A JP2007096831A JP2008214600A JP 2008214600 A JP2008214600 A JP 2008214600A JP 2007096831 A JP2007096831 A JP 2007096831A JP 2007096831 A JP2007096831 A JP 2007096831A JP 2008214600 A JP2008214600 A JP 2008214600A
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heavy metal
soil
heavy metals
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Shigemi Sakota
茂実 迫田
Yasuhiro Sakota
康博 迫田
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Abstract

<P>PROBLEM TO BE SOLVED: To provide microorganisms for the disposal of the heavy metal in soil and waste liquid. <P>SOLUTION: This method comprises the disposal in the soil and of the waste liquid and the disposal of the heavy metal to carry Bacillus natto and Actinomyces. Heavy metals include lead, cadmium, copper, iron, chromium, zinc, nickel, boron, and sodium. An example of Bacillus natto is a fungus of Bacillus subtilis. The disposal of the heavy metal using these useful microorganisms economically advantageously allows heavy metal disposal and soil improvement by mixture and agitation in this place to create an environment in which useful fungi can suitably proliferate without the need for an enormous cost and a maintenance expense. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

本発明は、土壌中及び廃液中の重金属を減少、除去処理するための環境浄化技術に関する。The present invention relates to an environmental purification technique for reducing and removing heavy metals in soil and waste liquid.

アルカリ金属のナトリウム以外の、重金属類は、非常に硬く融点1,000℃以上沸点1,000℃以上の元素類で中には、半導体の性質をもつ元素で、半金属元素に該当する物もある。
重金属類を人間や家畜が多量に摂取してしまうと、血圧低下、ショック症状や中枢神経抑制による呼吸停止があり、慢性中毒では、食欲不振、嘔吐、皮膚症状などを引き起こしてしまう。
このような化学的性質のもと、平成13年7月に水質汚濁防止法の一部改正、平成19年7月に施行予定では、「ホウ素及びその化合物」が追加された。それは、今までの基準値では排出限界値が500mg/lであったのが、改正後10mg/lとなり、環境基準値が1mg/lとなった。
また、カドミウムは、環境基準値が0.01mg/l、排水基準値が0.1mg/lと規制されている。
更に、食糧庁流通基準値では、0.4mg/l以上では食物としては流通禁止となっている。
それらを満足させる100m/円処理の機械式処理施設を建設するには、建設費が約1億円、維持費管理費用が年間約2000万円掛かる。
そこで本発明者は、より簡易で低価の重金属処理方法を開発し特許文献1において、アンモニア等を分解して悪臭が発生することのない動物飼育用床敷材料に関する技術を開示している。
Heavy metals other than sodium, an alkali metal, are very hard and have an melting point of 1,000 ° C. or higher and a boiling point of 1,000 ° C. or higher. Some of them have semiconducting properties and correspond to metalloid elements. is there.
If a large amount of heavy metals is ingested by humans or livestock, there is a decrease in blood pressure, shock symptoms, and respiratory arrest due to central nerve suppression, and chronic poisoning causes anorexia, vomiting, and skin symptoms.
Based on these chemical properties, “Boron and its compounds” were added in July 2001 when the Water Pollution Control Act was partially revised and scheduled to be implemented in July 2007. As for the standard value so far, the emission limit value was 500 mg / l, but after the revision it became 10 mg / l, and the environmental standard value became 1 mg / l.
Further, cadmium is regulated to have an environmental standard value of 0.01 mg / l and a drainage standard value of 0.1 mg / l.
Furthermore, according to the distribution standard value of the Food Agency, distribution is prohibited as food at 0.4 mg / l or more.
To construct a 100 m 3 / yen processing facility that satisfies them, construction costs are approximately 100 million yen, and maintenance costs are approximately 20 million yen per year.
In view of this, the present inventor has developed a simpler and less expensive heavy metal treatment method, and in Patent Document 1, discloses a technique relating to an animal breeding flooring material that does not decompose and deodorize ammonia and the like.

特許第3561693号公報  Japanese Patent No. 3561593

重金属含有の廃水から土壌が汚染されると、その汚染された土壌を直接摂取したり、汚染された土壌から有害物質が溶け出た地下水を飲用すること等により、人の健康に影響を及ぼすおそれがある。
こうした土壌汚染は、これまで明らかになることが少なかったが、近年企業の工業跡地等の再開発等に伴い、重金属、揮発性有機化合物等による土壌汚染が顕在化してきている。特に、最近における汚染事例の判明件数の増加は著しく、ここ数年で新たに判明した土壌汚染の事例数は高い水準であることから国民の健康への安全性にも課題となっていた。
If soil is contaminated from wastewater containing heavy metals, it may affect human health by directly ingesting the contaminated soil or drinking groundwater in which harmful substances are dissolved from the contaminated soil. There is.
Such soil contamination has been rarely clarified until now, but in recent years, with the redevelopment of industrial sites and the like of companies, soil contamination due to heavy metals, volatile organic compounds, etc. has become apparent. In particular, the recent increase in the number of known cases of contamination has been significant, and the number of newly discovered cases of soil contamination over the past few years has been a high level, which has also been an issue for public health safety.

また、食品加工産業においては、キムチ漬物や梅ぼし等の生産工程において、岩塩を用いることから岩塩中に微量の重金属及びナトリウムが含有していた。それらの廃水が地下水へ浸透したことによって、地下水に含まれる重金属及びナトリウムの量0.01ppm以上が人への安全性にも影響をおよぼす危険性がある。In the food processing industry, since rock salt is used in production processes such as kimchi pickles and umeboshi, trace amounts of heavy metals and sodium are contained in the rock salt. As the wastewater permeates into the groundwater, the amount of heavy metals and sodium contained in the groundwater of 0.01 ppm or more has a risk of affecting human safety.

本発明が解決しようとする課題は、土壌中及び廃液中の重金属を減少及び除去する微生物を用いた、土壌改良剤及び重金属処理技術を確立することにある。The problem to be solved by the present invention is to establish a soil conditioner and heavy metal treatment technology using microorganisms that reduce and remove heavy metals in soil and waste liquid.

本発明の微生物を用いた重金属処理技術は、木片や土と、もみ殻と焼却灰に、納豆菌(バチルスサブチルス)および放線菌を担持させてなることを特徴とする。The heavy metal processing technology using the microorganism of the present invention is characterized in that wood chips, soil, rice husks, and incinerated ash are loaded with Bacillus subtilis and actinomycetes.

本発明の重金属の減少及び除去方法は、土壌中および水溶液中において、含有する重金属を納豆菌(バチルスサブチルス含む)および放線菌が分解減少することでナトリウムを含む、重金属類の濃度が減少することを特徴とする。In the method for reducing and removing heavy metals according to the present invention, the concentration of heavy metals including sodium is reduced by decomposing and reducing natto bacteria (including Bacillus subtilis) and actinomycetes in the soil and in aqueous solutions. It is characterized by that.

本発明者で納豆菌と放線菌とを選択して組合せたものは、食品廃液の中でも重金属類を多く含むキムチ廃液を分解消滅させることを発見し、本発明に至ったものである。
すなわち納豆菌と放線菌では、優先種競合菌が1種類とはならずに相互に協調して、おのおのの効果を表わすことがあきらかになったからである。
The inventor has selected and combined natto and actinomycetes, and found that the kimchi waste liquid containing a large amount of heavy metals is decomposed and extinguished among the food waste liquids, resulting in the present invention.
In other words, it has become clear that, in Bacillus natto and Actinomycetes, the priority species competing bacteria do not become one type but cooperate with each other to express their effects.

当技術での特徴は、納豆菌と放線菌の胞子が互に協調することから、通常では雑菌の繁殖しにくい60℃以上0℃以下においても活動していることを確認している。また、海水中以上に塩分濃度の濃い塩分濃度40000mg/lの水溶液をも分解減少させている。
重金属類の減少・除去とは、土壌中や水溶液中においてナトリウムを含む重金属濃度が減少することを言う。
The feature of this technology is that the spore of Natto and Actinomycetes cooperate with each other, and it has been confirmed that they are active even at 60 ° C. or less and 0 ° C. or less, which is difficult for bacteria to propagate normally. In addition, an aqueous solution having a salinity of 40000 mg / l, which has a higher salinity than seawater, is also decomposed and reduced.
The reduction / removal of heavy metals means that the concentration of heavy metals including sodium decreases in soil or in aqueous solution.

本発明の最大の特徴は、納豆菌および放線菌を選択して重金属の減少材料に用いたことである。
これにより、重金属及び廃液を分解減少させることに温度を30℃以上にさせることと、通風させることで好気性菌である放線菌の活躍を維持させることができる。
The greatest feature of the present invention is that natto and actinomycetes are selected and used as a material for reducing heavy metals.
Thereby, the activity of actinomycetes, which are aerobic bacteria, can be maintained by increasing the temperature to 30 ° C. or more for decomposing and reducing heavy metals and waste liquid.

以下、本発明をその実施形態に基づいて説明する。
本発明の重金属処理材には、木片や土およびワラ・モミガラ材・焼却灰(石炭灰)等に納豆菌およびおよび放線菌を担持させており、これらの納豆菌及び放線菌が重金属類及び廃液を減少させている。放線菌はストレプトマイセン属等が挙げられる。重金属処理材料には、納豆菌および放線菌を混合して担持させることができ、或いはこれらを含む液状物を吹き付けて担持させて使用することもできる。重金属類等には少なくとも鉛・カドミウム・銅・クロム・砒素・ホウ素・亜鉛・ニッケル・ナトリウム等が挙げられる。
以下、実施例にして説明する。
Hereinafter, the present invention will be described based on the embodiments.
In the heavy metal treatment material of the present invention, natto bacteria and actinomycetes are supported on wood chips, soil, straw, pearwood, incineration ash (coal ash), etc., and these natto and actinomycetes are heavy metals and waste liquid. Is decreasing. Examples of actinomycetes include Streptomycene. The heavy metal treatment material can be supported by mixing natto and actinomycetes, or can be used by spraying a liquid material containing these. Heavy metals include at least lead, cadmium, copper, chromium, arsenic, boron, zinc, nickel, sodium, and the like.
Hereinafter, an example will be described.

重金属処理材の調整
重金属処理材としては、モミガラに納豆菌は10〜1012個/g、放線菌はストレプトマイセン属の菌を10〜10個/gとなるように添加して混合、湿度50〜90%温度30〜70℃の発酵機で6時間加熱混合して出来た担体を使用した。
A : モミガラ + 放線菌
B : モミガラ + 放線菌 + 納豆菌
C : モミガラ + 大腸菌
実施例としては、ホウ素とカドミウムを用いた。カドミウムの耐性のある菌株を得るためのスクリーニングを行った。
スクリーニングは、カドミウム含有(1000,1500,3000,5000,ppm)入りのNA培地PDA培地、それぞれにメッキ工場排水、汚泥水100μlを滴下して、30℃の恒温機にて菌が発育されるのを確認できるまで静置培養した。
その後、発育が確認されたカドミウム耐性菌株を用いて菌によるカドミウム除去が行われるかどうか50ppmのカドミウム含有培地で実験を行なった。菌株としては、「放線菌・納豆菌+放線菌・大腸菌」も用いた。
実験条件としては、カビは「バクトペプトン5g、グルコース2g、蒸留水1l」の培地とし、細菌はNB培地として、カドミウムイオン濃度が50ppm含有するように調整し、35℃5日間、70rpmで振とう培養した。
測定は、ICP・AFSで1日おきに10倍希釈したものを測定した。
Preparation of heavy metal treatment material As a heavy metal treatment material, add 10 3 to 10 12 natto bacteria / gram to Streptomyces and streptomycene bacteria to 10 3 to 10 7 bacteria / g. A carrier made by heating and mixing in a fermenter having a humidity of 50 to 90% and a temperature of 30 to 70 ° C. for 6 hours was used.
A: Momiji + actinomycetes B: Momiji + actinomycetes + Natto bacteria C: Momiji + Escherichia coli Boron and cadmium were used as examples. Screening to obtain strains resistant to cadmium was performed.
For screening, NA culture medium PDA medium containing cadmium (1000, 1500, 3000, 5000, ppm), plating factory effluent and 100 μl of sludge water are dropped into each, and the bacteria are grown in a thermostat at 30 ° C. The culture was stationary until it was confirmed.
Thereafter, an experiment was conducted using a 50 ppm cadmium-containing medium to determine whether cadmium removal by bacteria was performed using a cadmium-resistant strain that had been confirmed to grow. As the strain, “actinomycetes / natto bacteria + actinomycetes / Escherichia coli” were also used.
As experimental conditions, mold is a medium of “bactopeptone 5 g, glucose 2 g, distilled water 1 l”, bacteria is NB medium, adjusted to contain a cadmium ion concentration of 50 ppm, and shaken at 35 ° C. for 5 days at 70 rpm. Cultured.
The measurement was performed by diluting 10 times with ICP / AFS every other day.

Figure 2008214600
Figure 2008214600

試料Aにおいてホウ素は約20%と減少は少ないが、カドミウムが約50%除去されていることが確認された。
試料Bにおいて、ホウ素約30%、カドミウムが約70%除去されていることが確認された。
試料Cにおいて、ホウ素約20%、カドミウムが約40%除去されていることが確認された。
表1.によると、ホウ素については、約30%減少と効果が判然としなかった。特に放線菌を単独で用いた場合は、ホウ素は約20%の除去率であった。
納豆菌と放線菌を用いた試料Bにおいて、カドミウムが約70%除去されたことは重金属処理材として有望である。
In sample A, boron was reduced by about 20%, but it was confirmed that about 50% of cadmium was removed.
In Sample B, it was confirmed that about 30% of boron and about 70% of cadmium were removed.
In Sample C, it was confirmed that about 20% of boron and about 40% of cadmium were removed.
Table 1. According to the report, boron was reduced by about 30% and the effect was not clear. In particular, when actinomycetes were used alone, the removal rate of boron was about 20%.
In Sample B using natto and actinomycetes, about 70% of cadmium was removed, which is promising as a heavy metal treatment material.

実施例1で供試した試料A・B・Cについて、重金属を多種多量に含むキムチ廃液を用いた実験を行なった。
供試体厚さ5cmを15×15×5=1,125cc 容器に900cc(15×15×4)充填したバイオベッド。
キムチ廃液を毎日100ccバイオベッドに添加する。
The samples A, B, and C used in Example 1 were subjected to an experiment using kimchi waste liquid containing a large amount of heavy metals.
A biobed in which 900 cc (15 × 15 × 4) is filled in a specimen of 5 cm thickness, 15 × 15 × 5 = 1,125 cc container.
Kimchi waste liquid is added to the 100 cc biobed daily.

Figure 2008214600
Figure 2008214600

試料Aにおいて、クロムが17%、ニッケルが23%除去されていたことが確認された。
試料Bにおいて、クロムが35%でそれ以外の6項目で57%以上除去されたことが確認された。
試料Cにおいて、クロム、カドニウム、ニッケルが除去されていないことが確認された。
納豆菌と放線菌を用いた試料Bにおいて、6項目で50%以上が除去されたことは重金属処理剤として有望である。また、60日間においてキムチ廃液が延べ6000cc消滅処理されたことは、食品廃液処理剤として有望である。
In sample A, it was confirmed that 17% of chromium and 23% of nickel were removed.
In sample B, it was confirmed that chromium was removed by 35% and 57% or more was removed in the other 6 items.
In Sample C, it was confirmed that chromium, cadmium, and nickel were not removed.
In sample B using natto and actinomycetes, it is promising as a heavy metal treatment agent that 50% or more of 6 items have been removed. In addition, the fact that 6000 cc of kimchi waste liquid has been extinguished in 60 days is promising as a food waste liquid treatment agent.

土壌中の重金属を処理する土壌改良材は、動物の糞を30〜60、オガコ10〜30、もみがら20〜40、焼却灰(クリンカ等)20〜80重量部及び所定量の納豆菌と放線菌を混合し、ただし、前記所定量の納豆菌は、前記全混合物1g当たり菌数として1,000,000〜1,000,000,000個とし、ついで該混合物を30〜80%の相対湿度の発酵装置で60〜65℃の温度において混合過熱処理を施してこれを発酵させ3時間以上12時間以内において発酵させたものが食品廃液処理剤である。Soil improvers that treat heavy metals in soil are 30-60 animal droppings, 10-30 sawdust, 20-40 rice husks, 20-80 parts by weight incinerated ash (such as clinker), and a predetermined amount of Bacillus natto and radiation. The predetermined amount of natto bacteria is 1,000,000 to 1,000,000,000 per gram of the total mixture, and then the mixture has a relative humidity of 30 to 80%. A food waste liquid treatment agent is obtained by performing a mixed superheat treatment at a temperature of 60 to 65 ° C. in a fermenting apparatus and fermenting the mixture by heat for 3 hours to 12 hours.

まず、用意されたオガコ(5〜20mm)を10kgと、もみがら(5〜20mm)を40kg、焼却灰20kg及び納豆菌と放線菌を菌数として約20億個を混合物全体に約3〜6時間加温・通風、均等になるまでに十分に攪拌混合した。First, 10 kg of prepared sawdust (5 to 20 mm), 40 kg of rice husk (5 to 20 mm), 20 kg of incineration ash, and about 2 billion natto bacteria and actinomycetes in the total mixture, about 3 to 6 The mixture was thoroughly stirred until it was warmed and ventilated for a period of time and even.

混合加熱処理が終わって発酵装置から取り出された発酵生成物をして本発明の重金属処理材である。The fermented product taken out from the fermenter after the mixed heat treatment is finished is the heavy metal treatment material of the present invention.

重金属処理材で土壌改良の必要な処理区に1平方メートル当り約10g〜100gを散布する。均一に散布後、耕運機やトラクターで地表面から20cmの深さまで混合攪拌を行う。About 10 to 100 g per square meter is sprayed in a treatment area where soil improvement is necessary with a heavy metal treatment material. After spraying uniformly, mixing and stirring is performed to a depth of 20 cm from the ground surface with a cultivator or tractor.

本発明は、特別の動力源を用いず自然環境に悪影響を及ぼすことなく食品廃棄物の処理及び重金属などに汚染されている土壌中へ直接散布して混合攪拌することで土壌中の重金属や廃液中の重金属を減少させうる技術として広く利用することが出来る。The present invention does not use a special power source, and does not adversely affect the natural environment.It treats food waste and directly sprays it into soil contaminated with heavy metals, and mixes and agitates it. It can be widely used as a technique capable of reducing heavy metals in the inside.

Claims (5)

土壌中及び廃液中の微量重金属の除去に納豆菌および放線菌を吸着培養させた担体を設いることを特徴とする。微生物処理剤と重金属処理剤及び土壌改良剤。The present invention is characterized in that a carrier on which natto and actinomycetes are adsorbed and cultured is provided for removing trace heavy metals in soil and waste liquid. Microbial treatment agent, heavy metal treatment agent and soil conditioner. 前記重金属には、少なくとも鉛・カドミウム・銅・クロム・ヒ素・ホウ素・亜鉛・ニッケル・ナトリウムとが含まれる請求項1記載の重金属処理材。The heavy metal treatment material according to claim 1, wherein the heavy metal contains at least lead, cadmium, copper, chromium, arsenic, boron, zinc, nickel, and sodium. 土壌中の重金属の除去及び減少と同時に食品廃棄物(酒粕、焼酎粕、澱粉、漬物類の漬け汁等)や食品残渣をも減少及び消滅させることを可能とした微生物処理剤。A microbial treatment agent that can reduce and eliminate food waste (sake lees, shochu, starch, pickles of pickles, etc.) and food residues simultaneously with the removal and reduction of heavy metals in the soil. 土壌中において、現有する重金属類を減少させるために、納豆菌および放線菌を用いることを特徴とする重金属処理方法。A method for treating heavy metals, comprising using Bacillus natto and actinomycetes in order to reduce existing heavy metals in soil. 水溶液中の重金属とは、キムチ漬汁や漬物漬汁などの食品廃液や自動車、電機器、半導体、原水力発電所の制御棒などの廃液及び洗浄剤の重金属を含み、それらの含有濃度を減少させることを特徴とする重金属処理材。Heavy metals in aqueous solutions include waste liquids such as kimchi and pickles, waste liquids such as automobiles, electrical equipment, semiconductors, and control rods of raw hydroelectric power plants, and heavy metals used as cleaning agents. A heavy metal treatment material characterized in that
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Cited By (6)

* Cited by examiner, † Cited by third party
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CN102151690A (en) * 2011-01-20 2011-08-17 杭州大地环保有限公司 Method for treating arsenic sulfide residue
CN103205384A (en) * 2013-04-17 2013-07-17 广州利万世环保科技有限公司 Soil heavy metal hexavalent chromium biological degrading agent and production method thereof
CN103396963A (en) * 2013-07-29 2013-11-20 广州利万世环保科技有限公司 Soil heavy metal cadmium copper biodegradation agent and preparation method thereof
CN107446861A (en) * 2017-09-06 2017-12-08 北京双龙阿姆斯科技有限公司 Microbial bacterial agent of degraded heavy-metal residual and preparation method thereof
CN107722987A (en) * 2017-09-12 2018-02-23 上海圣珑环境修复技术有限公司 A kind of preparation of metal ion stabilizer and its restorative procedure to arable soil
CN109452554A (en) * 2018-12-17 2019-03-12 付斌 A kind of nourishing rice flour for babies and preparation method thereof

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102151690A (en) * 2011-01-20 2011-08-17 杭州大地环保有限公司 Method for treating arsenic sulfide residue
CN103205384A (en) * 2013-04-17 2013-07-17 广州利万世环保科技有限公司 Soil heavy metal hexavalent chromium biological degrading agent and production method thereof
CN103205384B (en) * 2013-04-17 2014-05-07 广州利万世环保科技有限公司 Soil heavy metal hexavalent chromium biological degrading agent and production method thereof
CN103396963A (en) * 2013-07-29 2013-11-20 广州利万世环保科技有限公司 Soil heavy metal cadmium copper biodegradation agent and preparation method thereof
CN107446861A (en) * 2017-09-06 2017-12-08 北京双龙阿姆斯科技有限公司 Microbial bacterial agent of degraded heavy-metal residual and preparation method thereof
CN107446861B (en) * 2017-09-06 2024-02-27 北京双龙阿姆斯科技有限公司 Microbial agent for degrading heavy metal residues and preparation method thereof
CN107722987A (en) * 2017-09-12 2018-02-23 上海圣珑环境修复技术有限公司 A kind of preparation of metal ion stabilizer and its restorative procedure to arable soil
CN109452554A (en) * 2018-12-17 2019-03-12 付斌 A kind of nourishing rice flour for babies and preparation method thereof

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