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CN106011045A - Method for preparing Sb-polluted site efficient ecological restoration flora by utilizing biogas residues - Google Patents

Method for preparing Sb-polluted site efficient ecological restoration flora by utilizing biogas residues Download PDF

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CN106011045A
CN106011045A CN201610370472.5A CN201610370472A CN106011045A CN 106011045 A CN106011045 A CN 106011045A CN 201610370472 A CN201610370472 A CN 201610370472A CN 106011045 A CN106011045 A CN 106011045A
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sulfate
antimonate
flora
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张大磊
李瑞栋
王欣玉
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Qingdao University of Technology
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Abstract

本发明提供一种利用沼渣制备Sb(V)污染场地高效生态修复菌群的方法,通过向沼渣中添加碳源及硫酸盐,使沼渣中硫酸盐还原菌群迅速生长,同时产生硫化物;随后加入锑酸盐,消耗抑制硫酸盐还原菌生长的硫化物,而硫化物的存在也大大降低了锑酸盐对硫酸盐还原菌的毒性,同时使所培养的硫酸盐还原菌群耐Sb性能提高。The invention provides a method for using biogas residues to prepare efficient ecological restoration flora of Sb(V) polluted sites. By adding carbon source and sulfate to biogas residues, the sulfate-reducing flora in biogas residues can grow rapidly and produce sulfide at the same time. Subsequent addition of antimonate consumes the sulfide that inhibits the growth of sulfate-reducing bacteria, and the presence of sulfide also greatly reduces the toxicity of antimonate to sulfate-reducing bacteria, and at the same time makes the cultured sulfate-reducing bacteria resistant to Sb performance improved.

Description

一种利用沼渣制备Sb污染场地高效生态修复菌群的方法A method of using biogas residues to prepare efficient ecological restoration flora of Sb-contaminated sites

技术领域 technical field

本发明提供一种利用沼渣制备Sb污染场地高效生态修复菌群的方法,通过向沼渣中添加碳源及硫酸盐,使沼渣中硫酸盐还原菌群迅速生长,同时产生硫化物;随后加入锑酸盐,消耗抑制硫酸盐还原菌生长的硫化物,而硫化物的存在也大大降低了锑酸盐对硫酸盐还原菌的毒性,同时使所培养的硫酸盐还原菌群耐Sb性能提高,属环境保护领域。 The invention provides a method for using biogas residues to prepare highly efficient ecological restoration flora of Sb-contaminated sites. By adding carbon sources and sulfates to biogas residues, the sulfate-reducing flora in biogas residues can grow rapidly and produce sulfide at the same time; Adding antimonate consumes sulfide that inhibits the growth of sulfate-reducing bacteria, and the presence of sulfide also greatly reduces the toxicity of antimonate to sulfate-reducing bacteria, and at the same time improves the Sb resistance of the cultured sulfate-reducing bacteria , which belongs to the field of environmental protection.

背景技术 Background technique

由于矿山开采、冶金废水任意排放,造成了大量土壤被Sb污染。目前处理含汞土壤的方法都有缺陷。高温熔融法成本高,耗能大。生物法反应周期长,且容易造成外来生物菌剂的二次污染。固化法效果不稳定,且固化剂容易对土壤造成二次污染。专利号201510056406.6介绍了一种含重金属土壤的固化方法,但该方法使用了大量的材料,成本较高,另一方面固化效果不稳定,如加入的氧化钙在自然条件下易发生碳酸化作用,使得碱性固化效果降低。 Due to the random discharge of mining and metallurgical wastewater, a large amount of soil is polluted by Sb. Current methods of treating mercury-containing soils are flawed. The high temperature melting method is costly and consumes a lot of energy. The biological method has a long reaction cycle and is likely to cause secondary pollution by foreign biological agents. The effect of the curing method is unstable, and the curing agent is likely to cause secondary pollution to the soil. Patent No. 201510056406.6 introduces a solidification method for soil containing heavy metals, but this method uses a large amount of materials, and the cost is high. On the other hand, the solidification effect is unstable. For example, the added calcium oxide is prone to carbonation under natural conditions. This reduces the effect of alkaline curing.

发明内容 Contents of the invention

针对现有技术的不足,本发明提供一种利用沼渣制备Sb(V)污染场地高效生态修复菌群的方法,通过向沼渣中添加碳源及硫酸盐,使沼渣中硫酸盐还原菌群迅速生长,同时产生硫化物;随后加入锑酸盐,消耗抑制硫酸盐还原菌生长的硫化物,而硫化物的存在也大大降低了锑酸盐对硫酸盐还原菌的毒性,同时使所培养的硫酸盐还原菌群耐Sb性能提高。 Aiming at the deficiencies of the prior art, the present invention provides a method of using biogas residues to prepare efficient ecological restoration flora of Sb(V) polluted sites, by adding carbon source and sulfate to biogas residues, so that sulfate-reducing bacteria in biogas residues The group grows rapidly and produces sulfide at the same time; then adding antimonate consumes the sulfide that inhibits the growth of sulfate-reducing bacteria, and the presence of sulfide also greatly reduces the toxicity of antimonate to sulfate-reducing bacteria, and at the same time makes the cultured The Sb-resistant performance of sulfate-reducing bacteria was improved.

其操作步骤如下: The operation steps are as follows:

(1)将沼渣与含一定量碳源的溶液混合,加入一定量的硫酸盐,放入反应器中进行生化反应,控制混合溶液干沼渣含量为0.1-20%,含固率0.5-25%,,有机碳含量0.5-20%,有机碳/硫酸盐(以SO4计)的质量比为(1-50):1,随后反应0.1-5天; (1) Mix biogas residue with a solution containing a certain amount of carbon source, add a certain amount of sulfate, and put it into a reactor for biochemical reaction. Control the content of dry biogas residue in the mixed solution to 0.1-20%, and the solid content to 0.5- 25%, the organic carbon content is 0.5-20%, the mass ratio of organic carbon/sulfate (calculated as SO4) is (1-50):1, and then reacted for 0.1-5 days;

(2)在步骤(1)反应后的溶液中,加入一定量的锑酸盐,控制硫酸盐/锑酸盐的摩尔比(1-50):1,有机碳/锑的质量比(10-100):1,随后反应0-5天; (2) in the solution after step (1) reaction, add a certain amount of antimonate, control the mol ratio (1-50) of sulfate/antimonate: 1, the mass ratio of organic carbon/antimony (10- 100): 1, followed by 0-5 days of reaction;

(3)重复向溶液中加锑酸盐0-4次,每次均控制硫酸盐/锑酸盐的摩尔比(1-50):1,有机碳/锑的质量比(10-100):1,反应时间0-5天,随后获得高效生态修复菌群。 (3) Repeatedly add antimonate to the solution 0-4 times, each time controlling the molar ratio of sulfate/antimonate (1-50):1, the mass ratio of organic carbon/antimony (10-100): 1. The reaction time is 0-5 days, and then high-efficiency ecological restoration flora can be obtained.

相比传统的含锑土壤处理方法,本方法有如下优势: Compared with traditional antimony-containing soil treatment methods, this method has the following advantages:

1.所培养的硫酸盐还原菌群本身为土著菌群,自然耐受力强,容易在场地大规模繁衍,有效还原锑酸盐的同时,不会造成生态问题; 1. The cultivated sulfate-reducing bacteria are indigenous flora, with strong natural tolerance, easy to reproduce on a large scale in the field, effectively reducing antimonate, and will not cause ecological problems;

2.培养驯化周期大大缩减,最快可1天内培养成,经济性大大提高; 2. The cultivation and acclimation cycle is greatly shortened, and it can be cultivated within 1 day at the fastest, and the economy is greatly improved;

3.在培养硫酸盐还原菌的同时,产生了代谢物硫化物,大大减轻随后添加的锑酸盐对硫酸盐还原菌的毒性,同时由于代谢物硫化物本身对硫酸盐还原菌就有抑制左右,因此这种方法在迅速培养硫酸盐还原菌的同时,增强了其耐锑特性; 3. While cultivating sulfate-reducing bacteria, the metabolite sulfide is produced, which greatly reduces the toxicity of the subsequently added antimonate to sulfate-reducing bacteria. At the same time, because the metabolite sulfide itself can inhibit sulfate-reducing bacteria, so This method not only rapidly cultivates sulfate-reducing bacteria, but also enhances its resistance to antimony;

4.Sb与硫酸盐还原菌代谢产物硫化物形成硫化Sb沉淀,使得土壤中Sb更加稳定。 4. Sb and sulfate-reducing bacteria metabolite sulfide form sulfide Sb precipitation, making Sb more stable in soil.

具体实施实例如下: The specific implementation examples are as follows:

实施例1: Example 1:

(1)将沼渣与含一定量碳源的溶液混合,加入一定量的硫酸盐,放入反应器中进行生化反应,控制混合溶液干沼渣含量为0.5%,含固率10%,,有机碳含量12%,有机碳/硫酸盐的质量比为5:1,随后反应1天; (1) Mix biogas residue with a solution containing a certain amount of carbon source, add a certain amount of sulfate, put it into a reactor for biochemical reaction, control the content of dry biogas residue in the mixed solution to 0.5%, and the solid content to 10%, The organic carbon content is 12%, and the mass ratio of organic carbon/sulfate is 5:1, followed by reaction for 1 day;

(2)在步骤(1)反应后的溶液中,加入一定量的锑酸盐,控制硫酸盐/锑酸盐的摩尔比(2-3):1,有机碳/锑的质量比(10-30):1,随后反应5天; (2) in the solution after step (1) reaction, add a certain amount of antimonate, control the mol ratio (2-3) of vitriol/antimonate: 1, the mass ratio of organic carbon/antimony (10- 30): 1, followed by reaction for 5 days;

(3)重复向溶液中加锑酸盐2次,每次均控制硫酸盐/锑酸盐的摩尔比(2-3):1,有机碳/锑的质量比(10-30):1,反应时间5天,随后获得高效生态修复菌群。 (3) Repeatedly adding antimonate 2 times in the solution, each time controlling the mol ratio (2-3) of sulfate/antimonate: 1, the mass ratio of organic carbon/antimony (10-30): 1, The reaction time was 5 days, and then the highly efficient ecological restoration flora was obtained.

实施例2: Example 2:

(1)将沼渣与含一定量碳源的溶液混合,加入一定量的硫酸盐,放入反应器中进行生化反应,控制混合溶液干沼渣含量为8-10%,含固率10-15%,,有机碳含量10-15%,有机碳/硫酸盐的质量比为20:1,随后反应0.1-1天; (1) Mix biogas residue with a solution containing a certain amount of carbon source, add a certain amount of sulfate, and put it into a reactor for biochemical reaction. Control the content of dry biogas residue in the mixed solution to be 8-10%, and the solid content to be 10- 15%,, the organic carbon content is 10-15%, the mass ratio of organic carbon/sulfate is 20:1, and then reacted for 0.1-1 day;

(2)在步骤(1)反应后的溶液中,加入一定量的锑酸盐,控制硫酸盐/锑酸盐的摩尔比(1-5):1,有机碳/锑的质量比(30-80):1,随后反应0-1天; (2) in the solution after step (1) reaction, add a certain amount of antimonate, control the mol ratio (1-5) of vitriol/antimonate: 1, the mass ratio of organic carbon/antimony (30- 80): 1, followed by reaction for 0-1 days;

(3)重复向溶液中加锑酸盐1次,控制硫酸盐/锑酸盐的摩尔比(1-5):1,有机碳/锑的质量比(30-80):1,反应时间1天,随后获得高效生态修复菌群。 (3) Repeatedly add antimonate to the solution once, control the molar ratio of sulfate/antimonate (1-5):1, the mass ratio of organic carbon/antimony (30-80):1, and the reaction time is 1 days, and then obtain highly efficient ecological restoration flora.

以上实施例仅用以说明本发明的技术方案,而非对其进行限制;尽管参照前述实施例对本发明进行了详细的说明,对于本领域的普通技术人员来说,依然可以对前述实施例所记载的技术方案进行修改,或者对其中部分技术特征进行等同替换;而这些修改或替换,并不使相应技术方案的本质脱离本发明所要求保护的技术方案的精神和范围。 The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art can still understand the foregoing embodiments. Modifications are made to the technical solutions described, or equivalent replacements are made to some of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions claimed in the present invention.

Claims (4)

1.一种利用沼渣制备Sb污染场地高效生态修复菌群的方法,其特征是,通过向沼渣中添加碳源及硫酸盐,使沼渣中硫酸盐还原菌群迅速生长,同时产生硫化物;随后加入锑酸盐,消耗抑制硫酸盐还原菌生长的硫化物,而硫化物的存在也大大降低了锑酸盐对硫酸盐还原菌的毒性,同时使所培养的硫酸盐还原菌群耐Sb性能提高,其包含以下步骤: 1. A method utilizing biogas residues to prepare efficient ecological restoration flora of Sb polluted sites is characterized in that, by adding carbon source and sulfate in biogas residues, sulfate-reducing flora in biogas residues is grown rapidly, and sulfide is produced simultaneously Subsequent addition of antimonate consumes the sulfide that inhibits the growth of sulfate-reducing bacteria, and the presence of sulfide also greatly reduces the toxicity of antimonate to sulfate-reducing bacteria, and at the same time makes the cultured sulfate-reducing bacteria resistant to Sb performance improvement, which includes the following steps: (1)将沼渣与含一定量碳源的溶液混合,加入一定量的硫酸盐,放入反应器中进行生化反应,控制混合溶液干沼渣含量为0.1-20%,含固率0.5-25%,,有机碳含量0.5-20%,有机碳/硫酸盐(以SO4计)的质量比为(1-50):1,随后反应0.1-5天; (1) Mix biogas residue with a solution containing a certain amount of carbon source, add a certain amount of sulfate, and put it into a reactor for biochemical reaction. Control the content of dry biogas residue in the mixed solution to 0.1-20%, and the solid content to 0.5- 25%, the organic carbon content is 0.5-20%, the mass ratio of organic carbon/sulfate (calculated as SO4) is (1-50):1, and then reacted for 0.1-5 days; (2)在步骤(1)反应后的溶液中,加入一定量的锑酸盐,控制硫酸盐/锑酸盐的摩尔比(1-50):1,有机碳/锑的质量比(10-100):1,随后反应0-5天; (2) in the solution after step (1) reaction, add a certain amount of antimonate, control the mol ratio (1-50) of sulfate/antimonate: 1, the mass ratio of organic carbon/antimony (10- 100): 1, followed by 0-5 days of reaction; (3)重复向溶液中加锑酸盐0-4次,每次均控制硫酸盐/锑酸盐的摩尔比(1-50):1,有机碳/锑的质量比(10-100):1,反应时间0-5天,随后获得高效生态修复菌群。 (3) Repeatedly add antimonate to the solution 0-4 times, each time controlling the molar ratio of sulfate/antimonate (1-50):1, the mass ratio of organic carbon/antimony (10-100): 1. The reaction time is 0-5 days, and then high-efficiency ecological restoration flora can be obtained. 2.如权利要求1所述的一种利用沼渣制备Sb污染场地高效生态修复菌群的方法,其特征是,所述的沼渣为农业、食品业有机废物进行干式、半干式及湿式厌氧发酵过程中的固体残留物。 2. a kind of method utilizing biogas residue to prepare Sb polluted site efficient ecological restoration flora as claimed in claim 1, is characterized in that, described biogas residue is agriculture, food industry organic waste carries out dry type, semi-dry type and Solid residues from wet anaerobic fermentation processes. 3.如权利要求1所述的一种利用沼渣制备Sb污染场地高效生态修复菌群的方法,其特征是,所述的碳源溶液可以为含有酒精、糖类、蛋白质、淀粉等有机物的溶液,也可以为含工业有机垃圾、餐厨垃圾等有机固体废物的溶液,也可以为工业及市政有机废水。 3. a kind of method utilizing biogas residues to prepare efficient ecological restoration flora of Sb polluted site as claimed in claim 1, is characterized in that, described carbon source solution can be that contains the organic matters such as alcohol, carbohydrate, protein, starch The solution may also be a solution containing organic solid waste such as industrial organic waste, kitchen waste, or industrial and municipal organic waste water. 4.如权利要求1所述的一种利用沼渣制备Sb污染场地高效生态修复菌群的方法,其特征是,所述的含硫酸盐为硫酸钠、硫酸钾、硫酸亚铁、硫酸铁等含硫酸根的盐类;所述锑酸盐为含有锑酸盐的盐类。 4. a kind of method utilizing biogas residue to prepare efficient ecological restoration flora of Sb polluted site as claimed in claim 1, is characterized in that, described sulfate-containing salt is sodium sulfate, potassium sulfate, ferrous sulfate, ferric sulfate etc. Salts containing sulfate; the antimonate is a salt containing antimonate.
CN201610370472.5A 2016-05-30 2016-05-30 Method for preparing Sb-polluted site efficient ecological restoration flora by utilizing biogas residues Pending CN106011045A (en)

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CN1332701A (en) * 1998-12-29 2002-01-23 帕克比奥系统公司 Process for treatment of waste water containing heavy metals
CN101195859A (en) * 2006-12-05 2008-06-11 中国科学院过程工程研究所 Technology of treating low concentration heavy metal sulfate solution by microbial method
CN104450552A (en) * 2014-08-17 2015-03-25 西北大学 Sulfate reducing bacteria-phosphate solubilizing bacteria and application thereof in combined remediation of cadmium contaminated soil

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Application publication date: 20161012