CN103396804B - A kind of oil-heavy-metal composite pollution salinization soil is repaired the preparation method of modifying agent - Google Patents
A kind of oil-heavy-metal composite pollution salinization soil is repaired the preparation method of modifying agent Download PDFInfo
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Abstract
The present invention relates to a kind of oil-heavy-metal composite pollution salinization soil and repair the preparation method of modifying agent. Carbon black is through airing, toner powder or granular darkly; Bacillus subtilis and Sphingobacterium multivorum two strain bacterium are mixed with to 8 × 10 by 1:110The composite bacteria of individual/ml; Natural pond slag is air-dry, pulverized after 10 mesh sieves, composite by a certain percentage with carbon black, urea, high efficient petroleum degrading bacteria; Adopt flat-die type powdered extruder grain, produce cylindrical particle, then throw circle through throwing circular knitting machine, vibratory sieve screening laggard enter cooler, cooling after through weighing pack. Modifying agent prepared by the inventive method, in utilizing the efficient degradation soil Petroleum Hydrocarbon of oil degradation bacteria, reduces the activity of heavy metal in oil degradation process; Promote plant growth on salinization soil, utilize plant to promote microbial degradation efficiency. The inventive method is that slight oil-heavy-metal contaminated soil microorganism-phytoremediation technology provides efficient, economic, a safe modifying agent.
Description
Technical field:
The present invention relates to a kind of preparation method who is applied to oil-heavy-metal composite pollution salinization soil original position reparation modifying agent.
Background technology:
Along with the demand of oil increases considerably, oil exploitation industrial boom. Oil pollution problem in the processes such as exploitation, transport, storage, processing is quite outstanding. China is as maximum in the world Petroleum Production and country of consumption, and the oil field of exploration and development has exceeded more than 500, and oil annual production has exceeded 1 × 1011Kg. Because each elephant region DP technology between past many decades falls behind relatively, seal is not good; in addition environmental protective measure falls behind, pollutes the reasons such as control and recovery technique shortage relatively; make China's soil petroleum-type pollution level far above developed country, and be year by year accumulation and increase the weight of situation.
Oil enterprises in China is produced ground crude oil approximately 700,000 t every year, and wherein approximately 70,000 t enter soil environment, and the subregion soil and groundwater deterioration of the ecological environment is to expendable edge. Daqing oil field oil development district contaminated soil area exceedes 75%, and around oil well, within the scope of 100m, in soil, average oil content reaches 1037mg/kg, far away higher than critical value 500mg/kg; In serious pollution district, Liaohe Oil Field, the oil content in soil has exceeded l0000mg/kg; The Shen Fu irrigated area, petroleum wastewater irrigated area of China's maximum, soil mineral oil in fluid concentration is up to 6861.1mg/kg(Li Xiao army etc., 2007). Delta Region of The Yellow River has abundant petroleum resources, is the second largest petroleum base of China. 47 exploratory spots that Qilu Petrochemical in 1993 is carried out oil-polluted soils region, totally 129 soil sample analyses show: petroleum-type organic pollution recall rate is 100%, total oil detects peak and reaches 900mg/kg, point position petroleum hydrocarbon content from oil well close to is up to 65000mg/kg, reservoir northwest, Guangnan, Mouth Area of The Yellow River to oil recovery field near in soil the quality percentage composition of total petroleum hydrocarbon and oil and fat can reach 0.35% and 2.4%; Polycyclic aromatic hydrocarbon in the deposit of the Huanghe delta is mainly derived from the crude oil pollution of the Huanghe delta. In addition, topsoil, Momoge marsh oilfield exploitation district of northwest of Jilin province ubiquity soil petroleum pollution etc. are polluted in the unprocessed direct stacking of the discarded slurry well site in most well sites, Shaanxi Chang Qing oil field. Petroleum-type is polluted has become one of principal mode of China's soil resource destruction.
The most onshore oil fields of China, the especially oil field of northern area, a more outstanding feature is exactly that soil salt content is generally higher, and vegetation pattern is simple, and especially soil may exist oil-heavy-metal composite pollution. Microorganism-phytoremediation technology has been considered to the oil-polluted soils recovery technique of most worthy and tool vitality. For avoiding when microorganism-Phytoremediation of Petroleum-polluted Soil, heavy metallic activation, simultaneously for improving remediation efficiency, in the urgent need to researching and developing the modifying agent of economy, safe, efficient, practical oil-heavy-metal composite pollution soil, to guarantee the remediation efficiency of microorganism-phytoremediation technology.
Summary of the invention:
The object of the invention is to overcome the shortcoming of prior art, a kind of preparation method who is applied to oil-heavy-metal composite pollution salinization soil original position reparation modifying agent is provided. The technology of the present invention is carried out proportioning with carbon black, high efficient petroleum degrading bacteria, organic matter, chemical fertilizer etc. first, obtains oil-heavy-metal composite pollution salinization soil original position and repairs modifying agent.
In order to realize foregoing invention object, the preparation method that a kind of oil-heavy-metal composite pollution salinization soil of the present invention is repaired modifying agent operates in accordance with the following steps:
The first step, carbon black is through airing, darkly toner powder or grain powdery;
Described carbon black is the solid waste after treatment of decolouring for food processing industry, iodine sorption value (mg/g) >=800; Serge blue decolouring (ml) >=7-8; PH value is 6-8; Moisture (%)≤10; Ash (%)≤5;
Second step, high efficient petroleum degrading bacteria preparation: bacillus subtilis (Bacillussubtillus) and Sphingobacterium multivorum (Sphingobacteriummultivolum) two bacterial strains are mixed with to 8 × 10 by 1:110The composite bacteria of individual/ml;
Bacterial classification derives from Shandong Province academy sciences Biology Research Institute (ZL200710013906.7).
The 3rd step, modifying agent composite: natural pond slag is air-dry, pulverized after 10 mesh sieves, composite with carbon black, urea, high efficient petroleum degrading bacteria, wherein, natural pond slag: carbon black: the percentage by weight of urea is 88:10:2; The gross weight of natural pond slag and carbon black and urea: high efficient petroleum degrading bacteria is 1:1(w/v kg/ml);
Described natural pond slag derives from intensive milk cattle cultivating factory, cow dung after marsh gas power generation, the residue in methane-generating pit through airing, grind, sieve, for subsequent use.
The 4th step, granulation: adopts flat-die type powdered extruder grain, produce cylindrical particle, then through throwing circular knitting machine twice throwing circle, each circle of throwing needs water spray 3 times, 5 seconds of at every turn spraying water, vibratory sieve screening laggard enter cooler, cooling after through weighing pack.
The inventive method is simple to operate, and cost is low, and the feature of the modifying agent of preparation is, in utilizing the efficient degradation soil Petroleum Hydrocarbon of oil degradation bacteria, to utilize carbon black to reduce the activity of heavy metal in oil degradation process; Utilize organic and fertilizer improvement soil, promote plant growth on salinization soil, utilize plant to promote microbial degradation efficiency. For slight oil-heavy-metal contaminated soil microorganism-phytoremediation technology provides efficient, economic, a safe modifying agent.
Brief description of the drawings:
Fig. 1 cultivates 60 days soil available Cd content figure for adding modifying agent;
Fig. 2 cultivates 60 days soil available Ni content figure for adding modifying agent;
Fig. 3 adds modifying agent to cultivate Cd petroleum contaminated soil degradation rate figure after 60 days;
Fig. 4 adds modifying agent to cultivate Ni petroleum contaminated soil degradation rate figure after 60 days.
Detailed description of the invention:
Below by specific embodiment, the inventive method is further elaborated.
Embodiment 1: oil-heavy-metal composite pollution salinization soil is repaired the preparation of modifying agent
The first step, carbon black is through airing, darkly toner powder or grain powdery; Carbon black iodine adsorption value (mg/g) >=800; Serge blue decolouring (ml) >=7-8; PH value is 6-8; Moisture (%)≤10; Ash (%)≤5. Carbon black, for after food processing industry sewage disposal, is solid waste.
Second step, near high efficient petroleum degrading bacteria preparation: contaminated soil, screening obtains bacillus subtilis (Bacillussubtillus) and Sphingobacterium multivorum (Sphingobacteriummultivolum) 2 strain bacteriums Shengli Oil Field producing well, and two strain bacterium are mixed with 8 × 10 by 1:110The composite bacteria of individual/ml;
The 3rd step, modifying agent composite: natural pond slag is air-dry, pulverized after 10 mesh sieves, composite with carbon black, urea, high efficient petroleum degrading bacteria, wherein, natural pond slag 880kg, modified carbon black 100kg, urea 20kg, high efficient petroleum degrading bacteria 1000ml(8 × 1010Individual/ml).
Natural pond slag derives from intensive milk cattle cultivating factory, cow dung after marsh gas power generation, the residue in methane-generating pit through airing, grind, sieve, for subsequent use.
The 4th step, granulation: adopts flat-die type powdered extruder grain, produce cylindrical particle, then through throwing circular knitting machine twice throwing circle, each circle of throwing needs water spray 3 times, 5 seconds of at every turn spraying water, vibratory sieve screening laggard enter cooler, cooling after through weighing pack.
It is as shown in table 1 that oil-heavy-metal composite pollution salinization soil that the inventive method makes is repaired modifying agent product parameters:
Table 1 modifying agent product parameters
Product is two kinds of pitchy, no foul smell round shaped grain shape (particle diameter is at 3.35mm-5.6mm >=70%) and loose, black powder shapes, and assay all meets national standard.
The formula contrast test that embodiment 2, oil-heavy-metal composite pollution salinization soil are repaired modifying agent
Oil-heavy-metal composite pollution salinization soil of the present invention repairs modifying agent formula and comparative example formula scheme is as shown in table 2:
Table 2 formula scheme
It is as shown in table 3 on the impact of tomato yield that oil-heavy-metal composite pollution salinization soil of the present invention is repaired modifying agent, comparative example 2 and formula of the present invention are significantly higher than comparative example 1 to tomato yield, consider that carbon black is conducive in oil degradation process heavy metal-passivated, therefore formulation selection of the present invention: the slag 88%+10% carbon black+2% urea+high efficient petroleum degrading bacteria agent of air-dry natural pond, wherein.
The impact of table 3 modifying agent on tomato yield
Embodiment 3: oil-heavy-metal composite pollution salinization soil is repaired the effect test of modifying agent
Testing program is as shown in table 4:
The experimental program of the different modifying agents of table 4
Note: in table, I represents 0.2% oil-10mgkg-1Cd simulation oil-heavy-metal composite pollution soil; II represents 0.2% oil-100mgkg-1Ni simulation oil-heavy-metal composite pollution soil.
Result of the test is as follows:
1, the impact of modifying agent on heavy metal in soil activity
Add modifying agent and cultivate 60 days soil available Cd, Ni content as shown in Figure 1-2. In Fig. 1 and Fig. 2, abscissa represents cultivated days, and ordinate represents respectively soil available Cd and available and total Ni content (mg/kg). Fig. 1, Fig. 2 show, on 0.2% oil-10mg/kgCd or 0.2% oil-100mg/kgNi combined pollution salinization soil, add modifying agent and can suppress the activation of oil degradation heavy metals in process, and along with the increase of modifying agent addition activity decreased.
2, the impact of modifying agent on soil oil degradation
Add modifying agent and cultivate Cd after 60 days, Ni petroleum contaminated soil degradation rate as shown in Figure 3-4. In Fig. 3, ordinate represents petroleum hydrocarbon degradation rate (%); In abscissa, CK indicates without exogenous heavy metal soil; Cd10 represents to add the soil that heavy metal Cd concentration is 10mg/kg; CK-2% modifying agent indicates that without exogenous heavy metal while modifying agent applied amount be 2%; CK-4% modifying agent indicates that without exogenous heavy metal while modifying agent applied amount be 4%; The soil that Cd10-interpolation heavy metal Cd concentration is 10mg/kg; Cd10-2% modifying agent represents that external source Cd concentration is that 10mg/kg while modifying agent applied amount is 2%; Cd10-4% modifying agent represents that external source Cd concentration is that 10mg/kg while modifying agent applied amount is 4%. In Fig. 4, ordinate represents petroleum hydrocarbon degradation rate (%); In abscissa, CK indicates without exogenous heavy metal soil; Ni100 represents to add the soil that heavy metal Ni concentration is 100mg/kg; CK-2% modifying agent indicates that without exogenous heavy metal while modifying agent applied amount be 2%; CK-4% indicates that without exogenous heavy metal while modifying agent applied amount be 4%; It is that 100mg/kg while modifying agent applied amount is 2% that Ni100-2% modifying agent represents to add heavy metal Ni concentration; It is that 100mg/kg while modifying agent applied amount is 4% that Ni100-4% modifying agent represents to add heavy metal Ni concentration.
Fig. 3, Fig. 4 show, on 0.2% oil-10mg/kgCd or 0.2% oil-100mg/kgNi combined pollution salinization soil, add modifying agent and can increase petroleum degradation rate, and the effect of adding 2% modifying agent is best.
3, the impact of modifying agent on phytomass, as shown in table 5:
Table 5 applies the impact of modifying agent on phytomass
On 0.2% oil-10mg/kgCd or 0.2% oil-100mg/kgNi combined contamination soil, add 2%, 4% modifying agent, plant shoot fresh weight and dry weight all increase with the addition of modifying agent. Illustrate that adding modifying agent can improve edaphic condition, Promoting plant growth.
Claims (1)
1. the preparation method that oil-heavy-metal composite pollution salinization soil is repaired modifying agent, operation in accordance with the following steps: the first step, carbon black is through airing, toner powder or granular darkly, described carbon black is the solid waste after treatment of decolouring for food processing industry, iodine sorption value >=800mg/g; Serge blue decolouring >=7-8ml; PH value is 6-8; Moisture≤10%; Ash≤5%; Second step, high efficient petroleum degrading bacteria preparation: bacillus subtilis and Sphingobacterium multivorum two bacterial strains are mixed with to 8 × 10 by 1:110The composite bacteria of individual/ml; The 3rd step, modifying agent composite: natural pond slag derives from intensive milk cattle cultivating factory, cow dung after marsh gas power generation, the residue in methane-generating pit through air-dry, pulverized after 10 mesh sieves, composite with carbon black, urea, high efficient petroleum degrading bacteria; The 4th step, granulation: adopts flat-die type powdered extruder grain, produce cylindrical particle, then through throwing circular knitting machine twice throwing circle, each circle of throwing needs water spray 3 times, 5 seconds of at every turn spraying water, vibratory sieve screening laggard enter cooler, cooling after through weighing pack; The parameter of its soil remediation modifying agent of preparing is nitrogen content 2.3%; Available phosphorus content is with P2O5Count 1.5%; Potassium oxide content is with K2O counts 3.4%; Total nutrient N-P2O5-K2The mass fraction of O counts 7.2% to dry base; Quality of organic matter mark counts 47% to dry base; Free water content 25%; Acid-base value is 7.3; Living bacteria count is 4.1 hundred million/g; Product is pitchy, no foul smell round shaped grain shape, wherein particle diameter 3.35mm-5.6mm >=70%, meet national standard; In soil, add modifying agent and can improve tomato yield 16.02%, can suppress the activation of oil degradation heavy metals in process, increase petroleum degradation rate, improve edaphic condition, Promoting plant growth; It is characterized in that the natural pond slag in the 3rd step: carbon black: the percentage by weight of urea is 88:10:2; The gross weight of natural pond slag and carbon black and urea: high efficient petroleum degrading bacteria consumption is 1kg:1ml.
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| CN104649848A (en) * | 2015-03-06 | 2015-05-27 | 天津理工大学 | Solid bacterial fertilizer for remedying petroleum polluted saline alkali soil and preparation method of solid bacterial fertilizer |
| CN104759459B (en) * | 2015-04-07 | 2017-06-23 | 山东师范大学 | High concentration petroleum pollution soil dystopy in-situ combination biological renovation method |
| CN107896915B (en) * | 2017-09-25 | 2020-08-25 | 浙江海洋大学 | Artificial soil formula for preventing petroleum diffusion |
| CN109174906B (en) * | 2018-08-31 | 2021-04-27 | 浙江理工大学 | Device and method for solidifying fly ash |
| CN109609133A (en) * | 2018-11-09 | 2019-04-12 | 河南正达环保科技有限公司 | Oil-polluted soils repair materials |
| CN109576186A (en) * | 2018-12-27 | 2019-04-05 | 天津天丰泽田生物科技有限公司 | A kind of petroleum hydrocarbon degradation composite bacteria agent and preparation method thereof |
| CN109438088A (en) * | 2018-12-27 | 2019-03-08 | 天津天丰泽田生物科技有限公司 | A kind of microbe soil conditioner and preparation method thereof for remedying oil-polluted soils |
| CN112410265A (en) * | 2020-12-09 | 2021-02-26 | 鞍钢集团矿业有限公司 | Microbial agent and method for planting plants to improve tailing sand |
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| CN101050435A (en) * | 2007-03-16 | 2007-10-10 | 山东省科学院生物研究所 | Solid microbe agent for degrading petroleum pollution, and petroleum products, and preparation method |
| CN103084153A (en) * | 2013-01-18 | 2013-05-08 | 山东师范大学 | Method for preparing nano black carbon passivator for repairing heavy metal contaminated soil |
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| CN101050435A (en) * | 2007-03-16 | 2007-10-10 | 山东省科学院生物研究所 | Solid microbe agent for degrading petroleum pollution, and petroleum products, and preparation method |
| CN103084153A (en) * | 2013-01-18 | 2013-05-08 | 山东师范大学 | Method for preparing nano black carbon passivator for repairing heavy metal contaminated soil |
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