CN114058377B - Soil remediation agent and soil remediation method - Google Patents
Soil remediation agent and soil remediation method Download PDFInfo
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Abstract
The invention relates to the technical field of soil remediation, in particular to a soil remediation agent and a method for remediating soil. The soil remediation agent comprises the following components in parts by weight: 0.4-1.5 parts of soil modifier, 0.5-3 parts of nutrient, 0.1-0.5 part of slow-release oxygen agent and 0.5-3 parts of compound microbial agent. The soil repairing agent can improve the repairing capability of microorganisms, shorten the repairing period, improve the repairing efficiency and greatly reduce the repairing cost.
Description
Technical Field
The invention relates to the technical field of soil remediation, in particular to a soil remediation agent and a soil remediation method.
Background
In the prior art, technical means for remediation of petroleum-contaminated soil can be broadly classified into physical, chemical and microbiological methods. Wherein, the physical restoration mainly comprises a soil-burning method, an incineration method, a thermal desorption method, a gas-phase extraction method, an electrokinetic method and the like; the chemical repair mainly comprises a leaching method, an extraction method, a chemical oxidation method and the like.
However, the physical repair method generally requires a specific site and specialized mechanical equipment, and the chemical repair method requires the use of a large amount of chemical agents, both of which have high repair costs and are very prone to secondary pollution.
The microbial remediation method has the advantages of low cost, small influence on the environment, good treatment effect, no secondary pollution and the like, and is increasingly applied to remediation of the petroleum-polluted soil.
However, conventional microorganisms have limited repair ability, and have disadvantages of long repair cycle, low treatment efficiency, high repair cost, and the like.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a soil repairing agent, which can improve the repairing capability of microorganisms, shorten the repairing period, improve the repairing efficiency and greatly reduce the repairing cost.
The second purpose of the invention is to provide a method for restoring soil, which can rapidly degrade pollutants in the polluted soil by adopting an oxygen release technology and a biological stimulation technology and adopting a compound microbial agent and has the advantages of high restoration speed, short period, high efficiency, low cost and the like.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the invention provides a soil remediation agent, which comprises the following components in parts by weight:
0.4-1.5 parts of soil modifier, 0.5-3 parts of nutrient, 0.1-0.5 part of slow-release oxygen agent and 0.5-3 parts of compound microbial agent.
According to the soil remediation agent provided by the invention, by adopting the compound microbial agent, compared with a single microorganism, the compound microbial agent can efficiently decompose different kinds of pollutants in soil, so that a better remediation effect is obtained, the remediation period of the soil is shortened, and the treatment efficiency is improved.
In addition, the slow-release oxygen agent is added into the soil remediation agent, and oxygen released by the slow-release oxygen agent is used as an electron acceptor for pollutant decomposition in the microbial remediation process, so that the treatment efficiency of microbial remediation can be improved. This is because, during the remediation of contaminated soil by microorganisms, the degradation rate and degree of contaminants are greatly affected by the type and concentration of the final electron acceptor in the soil from which the contaminants are oxidatively decomposed. In the prior art, in order to ensure sufficient oxygen, the conventional soil microbial remediation technology needs to regularly turn over the soil remediation pile, however, the complexity of microbial remediation is increased, the pile height of the pile is limited, and the oxygen content in the bottom soil is difficult to ensure by an overhigh pile in the turning process. Therefore, the slow-release oxygen agent is added into the soil repairing agent, so that oxygen can be released to serve as an electron acceptor for decomposing petroleum hydrocarbon in the microbial repairing process, the turning frequency and the process complexity of stack maintenance can be greatly reduced, and meanwhile, the stack can be highly stacked to be higher, so that the microbial repairing treatment efficiency is improved, and the treatment cost is greatly reduced.
Meanwhile, the soil modifier and the nutrient are added, so that the propagation and growth of microorganisms can be stimulated, the activity of the microorganisms is improved, and the degradation capability of the microorganisms to pollutants is enhanced. In addition, the soil conditioner can increase the ventilation effect of the soil.
In conclusion, the soil remediation agent provided by the invention can improve the remediation capability of microorganisms, shorten the remediation period, improve the remediation efficiency and greatly reduce the remediation cost by adopting the soil conditioner, the nutrient, the slow-release oxygen agent and the compound microbial agent with specific dosage.
In some specific embodiments of the present invention, the soil property improving agent may also be selected from 0.46 parts, 0.5 parts, 0.6 parts, 0.8 parts, 1.0 parts, 1.1 parts, 1.2 parts, 1.3 parts or 1.4 parts; the nutrient can also be selected from 0.6 part, 0.8 part, 1 part, 1.2 parts, 1.5 parts, 1.7 parts, 1.9 parts, 2 parts, 2.3 parts, 2.4 parts, 2.7 parts or 2.9 parts; the slow release oxygen agent can also be selected from 0.2 part, 0.3 part or 0.4 part; the compound microbial agent can also be selected from 0.6 part, 0.8 part, 1 part, 1.2 parts, 1.5 parts, 1.7 parts, 1.9 parts, 2 parts, 2.3 parts, 2.4 parts, 2.7 parts or 2.9 parts.
Preferably, the compound microbial agent mainly comprises bacillus subtilis, pseudomonas and bacillus licheniformis.
The composite microbial agent is beneficial to further improving the degradation capability of pollutants and improving the treatment efficiency.
In some specific embodiments of the invention, the compound microbial agent is a compound indigenous microbial agent product, the type of which is MSTN-HT-004, and the manufacturer is Beijing Meiston science and technology development Co.
The bacillus subtilis, the pseudomonas and the bacillus licheniformis in the compound microbial agent of the type produced by the company are obtained by separating and domesticating soil polluted by petroleum hydrocarbon.
The petroleum hydrocarbon is a generic term of petroleum hydrocarbon compounds, and refers to hydrocarbon compounds in petroleum, namely hydrocarbons, including n-alkanes, branched alkanes, cycloalkanes, aromatic hydrocarbons and the like, which account for the vast majority of petroleum and are about tens of thousands of hydrocarbons.
Furthermore, in the compound microbial agent of the type produced by the company, bacillus subtilis is derived from petroleum hydrocarbon contaminated soil in a Jidong oil field, pseudomonas is derived from petroleum hydrocarbon contaminated soil in a Daqing oil field, and bacillus licheniformis is derived from petroleum hydrocarbon contaminated soil in a Clarity oil field.
In the prior art, the conventional soil microbial remediation adopts a single microorganism for remediation, and few single microorganisms have the capacity of degrading multiple pollutants, so that the lower limit of microbial remediation is limited. The biodegradation of petroleum hydrocarbons is usually carried out in multiple steps, in which multiple enzymes and multiple microorganisms are required, and the product of one enzyme or microorganism can become the substrate of another.
The bacillus subtilis, the pseudomonas and the bacillus licheniformis are respectively derived from petroleum hydrocarbon polluted soil of a Jidong oil field, a Daqing oil field and a Claritian oil field, indigenous bacteria capable of degrading various types of petroleum are separated and domesticated by a microorganism selective screening technology, and the treatment efficiency and the treatment capacity of the composite microbial agent are far beyond those of conventional indigenous bacteria.
Therefore, the composite microbial agent consisting of the bacillus subtilis, the pseudomonas and the bacillus licheniformis which are obtained by separating and domesticating the specific soil can decompose different kinds of petroleum hydrocarbons in the soil more efficiently and comprehensively, so that the better remediation effect is obtained, the remediation period of the soil containing the petroleum hydrocarbons is shortened, and the remediation efficiency is improved.
Furthermore, the total number of colonies of the compound microbial agent produced by the company is more than or equal to 5 multiplied by 10 8 one/mL.
Preferably, the mass ratio of the soil (the soil to be repaired) to the soil remediation agent is 100: 1-10 (1.5, 2, 3,4, 5, 6, 7, 8 or 9 can be selected), and more preferably 100: 1.5-8.
The mass ratio in the range is favorable for further improving the repair efficiency and reducing the repair cost.
Preferably, the soil modifier comprises rice hulls and/or straws; more preferably a mixture of the two.
The invention adopts rice hulls and/or straws as the soil conditioner, can further increase the ventilation effect of soil, and simultaneously, the rice hulls and the straws are also slow-release nutrient sources.
Preferably, the slow release oxygen agent comprises calcium peroxide.
The calcium peroxide is a slow-release oxygen agent, the speed of releasing oxygen is slow, the release period is long, in the microbial remediation process, the oxygen slowly released by the calcium peroxide can be used as an electron acceptor for decomposing pollutants, and meanwhile, waste caused by direct entering of the oxygen released too fast into the atmospheric environment can be avoided.
During the microbial remediation of contaminated soil, the type and concentration of the final electron acceptor of the oxidative decomposition of the contaminants in the soil greatly influence the degradation speed and degree of the contaminants. In the prior art, the electron acceptor provided by the conventional soil microorganism remediation technology for microorganisms is oxygen, and in order to provide sufficient oxygen, the soil remediation pile needs to be ploughed regularly. However, this adds complexity to microbial remediation and limits the heap height of the heap, as it is difficult to ensure the oxygen content of the base soil during the turn-up process.
Therefore, the invention introduces the slow-release oxygen agent, by adding a proper amount of the slow-release oxygen agent into the soil in the soil pretreatment process and controlling the period of the slow-release oxygen agent for releasing oxygen in the oil-containing soil, the slow-release oxygen agent can slowly release oxygen as an electron acceptor for decomposing petroleum hydrocarbon in the microbial remediation process, and simultaneously, the waste caused by the fact that the oxygen is released too fast and directly enters the atmospheric environment can be avoided.
Therefore, the slow-release oxygen agent is introduced, so that the turning frequency of stack maintenance can be greatly reduced, the process complexity is reduced, and meanwhile, the stack can be highly stacked to be higher, so that the treatment efficiency of microbial remediation is improved, and the treatment cost is greatly reduced.
In addition, the invention adopts the calcium peroxide, which can be gradually and slowly decomposed in humid air or soil with certain humidity, so that oxygen can be released for a long time, and the calcium peroxide is nontoxic and can not pollute the environment; meanwhile, calcium hydroxide generated after oxygen is released can be used with CO generated by the indigenous bacteria decomposing petroleum hydrocarbon 2 Calcium carbonate is generated by the reaction, and neither the intermediate product calcium hydroxide nor the final product calcium carbonate can generate adverse effects on the environment.
The following is the absorption of CO by the intermediate product of the calcium peroxide oxygen releasing machine 2 The equation of (2):
2CaO 2 +2H 2 O→2Ca(OH) 2 +O 2 ↑；
CO 2 +Ca(OH) 2 ═CaCO 3 ↓+H 2 O。
preferably, the nutrient comprises the following components in parts by weight:
10-20 parts of nitrogenous fertilizer, 30-50 parts of phosphate fertilizer, 10-20 parts of secondary elements, 15-25 parts of diatomite and 5-15 parts of cellulose;
preferably, the nitrogen fertilizer comprises urea;
preferably, the phosphate fertilizer comprises at least one of monopotassium phosphate, calcium phosphate and dipotassium phosphate; more preferably a mixture of the three;
preferably, the secondary element comprises at least one of calcium carbonate, calcium chloride and magnesium sulfate, more preferably a mixture of the three.
Wherein, the cellulose mainly plays a role in slow release nutrition and soil texture improvement.
The diatomite has the effects of moisturizing, loosening soil and prolonging the action time of the nutritional agent.
The nutrient provided by the invention is an aerobic biological repairing medicament, which is a composite formula repairing medicament formed by applying a biological stimulation principle and can be applied in the implementation forms of land cultivation and biological heap.
In most of petroleum hydrocarbon polluted soil, particularly after the pollution occurs for a period of time, the indigenous microorganisms for degrading the petroleum hydrocarbon which naturally exist are enriched, so that the deficiency of the indigenous bacteria for degrading the petroleum hydrocarbon is not a restriction factor for repairing the petroleum hydrocarbon polluted soil, but other conditions such as severe lack of nitrogen and phosphorus nutrition are used, therefore, under the condition, the nutrient is added to stimulate the reproduction and growth of the indigenous microorganisms, improve the activity of the indigenous microorganisms, remarkably enhance the degradation capability of the indigenous microorganisms on pollutants and further improve the treatment efficiency of the composite microbial agent.
The invention also provides a method for repairing soil, which uses the soil repairing agent and comprises the following steps:
the soil remediation agent is evenly mixed with the soil.
According to the method for restoring the soil, the oxygen release technology is adopted, the slow-release oxygen agent is added into the polluted soil, oxygen is released in the soil processing process, the plowing frequency and the process complexity of stack maintenance can be reduced, the stack can be highly stacked to be higher, the processing efficiency of microbial restoration is improved, and the processing cost is greatly reduced.
Moreover, by adopting a biostimulation technology (a technology for stimulating the reproduction and growth of indigenous microorganisms and improving the activity of the indigenous microorganisms and further enhancing the degradation capability of the indigenous microorganisms to target pollutants by improving and correcting the environmental and geological chemical conditions, such as adding a nutrient and a soil conditioner to soil, adjusting the appropriate temperature, humidity, pH value and the like), the indigenous microorganisms are added into the polluted soil, so that sufficient nutrition is provided for the growth of indigenous bacteria, the reproduction and growth of the indigenous microorganisms can be stimulated, the activity of the indigenous microorganisms is improved, and further the pollutants in the polluted soil are rapidly degraded.
Meanwhile, by adding the compound microbial agent, different kinds of pollutants in the soil can be efficiently and comprehensively decomposed, a better repairing effect is obtained, the repairing efficiency is improved, and the repairing period of the soil is shortened.
Therefore, the method for restoring the soil has the advantages of simple operation, high restoring speed, short period, high efficiency, low cost and the like.
Preferably, the soil comprises soil contaminated with petroleum hydrocarbons; more preferably, the compound microbial agent comprises bacillus subtilis, pseudomonas and bacillus licheniformis, wherein the bacillus subtilis, the pseudomonas and the bacillus licheniformis are obtained by separating and domesticating soil polluted by petroleum hydrocarbon; still more preferably, the bacillus subtilis is derived from contaminated soil in oil fields in the east of Ji, the pseudomonas is derived from contaminated soil in oil fields in the Chongqing, and the bacillus licheniformis is derived from contaminated soil in oil fields in Clarity.
Although the indigenous microorganisms widely exist in the petroleum hydrocarbon polluted soil, the indigenous microorganisms have the characteristics of low basic number, slow growth speed, long multiplication period and the like in the soil, and if the petroleum hydrocarbon polluted soil is only repaired by adopting the biostimulation effect, the whole repair period is long. Therefore, the application adopts a biological stimulation technology and a biological adding technology, and the composite indigenous bacteria are proliferated in a large quantity and returned to the original petroleum hydrocarbon polluted soil through a microorganism selective culture technology, so that the microorganisms can decompose different kinds of petroleum hydrocarbons in the soil efficiently and comprehensively to obtain a better repairing effect.
Preferably, the method specifically comprises the following steps:
(a) uniformly mixing soil, a soil conditioner, a nutrient, a slow-release oxygen agent and a compound microbial agent, and composting;
(b) uniformly mixing soil, a soil conditioner, a nutrient, a slow-release oxygen agent and a compound microbial agent, placing the mixture on the surface of the soil obtained in the step (a), and continuously performing composting treatment;
(c) and (c) obtaining the repaired soil after the soil obtained in the step (b) is detected to be qualified.
Wherein the composting treatment is a process of promoting aerobic decomposition and stabilization of organic matters by using microorganisms.
Preferably, the detecting specifically includes: sampling the biological piles obtained in the step (b) every 25-35 days (26 days, 27 days, 28 days, 29 days, 30 days, 31 days, 32 days, 33 days or 34 days can be selected), detecting the oil content in the biological piles, arranging sampling points on each pile as a detection unit, taking 3-5 soil at each point for mixed detection, and when the earth volume of the pile is more than 1000m 3 When it is used, per 1000m 3 Sampling a sample, if the detection is qualified, finishing the treatment of the pile, and if the detection is not qualified, continuing the treatment process until the detection is qualified.
Preferably, in step (a) and/or step (b), the soil is subjected to a crushing and screening treatment;
the treatment efficiency is improved and the repair period is shortened by crushing and screening.
More preferably, the crushing and sieving is performed using an ALLU sieving hopper.
Preferably, the particle size of the screened soil is less than 1.5cm, and 1.4cm, 1.3cm, 1.2cm, 1.1cm, 1.0cm, 0.8cm, 0.7cm, 0.5cm, 0.3cm, 0.2cm or 0.1cm can also be selected.
Preferably, in step (a), the height of the pile is 45-55 cm, including but not limited to the point value of any one of 46cm, 47cm, 48cm, 49cm, 50cm, 51cm, 52cm, 53cm, 54cm or a range value between any two.
Preferably, in step (b), the height of the pile is 90-110 cm, including but not limited to the point value of any one of 91cm, 93cm, 95cm, 97cm, 99cm, 100cm, 102cm, 105cm, 107cm, 109cm or a range value between any two.
In step (a) and/or step (b), the stacking time can be any conventional stacking time, and can be determined according to site construction conditions.
The invention adopts the slow-release oxygen technology, namely, the special type of slow-release oxygen agent is adopted, so that the oxygen is slowly released in the soil treatment process, the plowing frequency of the pile body can be reduced, the height of the pile body can be improved, and the treatment efficiency of microbial remediation can be improved.
Preferably, in step (a) and/or step (b), the oxygen content in the soil is monitored, the contents of carbon, nitrogen and phosphorus in the soil are monitored, and the temperature, pH and water content of the soil are monitored;
preferably, the mass ratio of the carbon element to the nitrogen element to the phosphorus element in the soil is 90-110: 5-15: 1; 95-105: 7-12: 1 can be selected; more preferably 100:10: 1.
Preferably, the temperature of the soil is 25-40 ℃, including but not limited to any one of 26 ℃, 27 ℃, 28 ℃, 29 ℃, 30 ℃, 33 ℃, 35 ℃ and 38 ℃ or a range value between any two;
preferably, the pH of the soil is 6.0 to 7.8, including but not limited to a point value of any one of 6.2, 6.5, 6.7, 7.0, 7.2, 7.5, 7.6, 7.7 or a range value between any two;
more preferably, the pH of the soil is adjusted by lime, ammonium sulphate or aluminium sulphite. Specifically, when the pH value of the soil is too low, a proper amount of lime is added to adjust the pH value; when the pH value of the soil is too high, ammonium sulfate or aluminum sulfite is added to adjust the pH value.
Preferably, the moisture content of the soil is between 25% and 35%, including but not limited to any one of 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, or a range between any two.
The invention adopts the biostimulation technology to improve the environmental geological conditions, adjust the temperature, the humidity, the pH value and the like of soil, stimulate the reproduction and the growth of indigenous microorganisms and improve the activity of the indigenous microorganisms, thereby enhancing the degradation capability of the indigenous microorganisms on pollutants.
Therefore, the temperature, the pH value and the water content are adopted, so that the repair capability of microorganisms is further improved, and the repair effect of the microorganisms on polluted soil is further improved.
Preferably, in step (a) and/or step (b), the soil and components are mixed homogeneously by at least one turn;
preferably, the number of plowing can also be selected from 2, 3,4, 5, 6, 7, 8 or 10.
Preferably, the number of plowing is controlled so that the oxygen content in the soil is greater than or equal to 7%, including but not limited to the point value of any one of 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 17%, 20% or the range value between any two.
More preferably, said turning is performed by a rotary cultivator.
The plowing is a soil farming method in which furrow soil is scooped up, loosened and turned over by using farm implements such as a plow, and is generally called plowing, plowing or plowing.
More preferably, in the step (a) and/or the step (b), the step of uniformly mixing the soil, the soil conditioner, the nutrient, the slow-release oxygen agent and the compound microbial agent specifically comprises: firstly, mixing soil and a soil conditioner, and uniformly stirring, wherein the soil conditioner is a slow-release nutrient source while increasing the ventilation effect of the soil; then spreading a nutrient and a sustained-release oxygen agent to play roles of biological stimulation and an electron acceptor; spraying a compound microbial agent into the biological reactor to obtain a first layer of biological pile; and then the rotary cultivator is used for turning and homogenizing the first layer of the biological pile.
In some specific embodiments of the present invention, the method for remediating soil specifically comprises:
firstly, selecting an area with smooth ground and relatively high terrain as a biological pile stacking area, measuring and laying lines to draw an accurate area of a biological pile stacking body, leveling the area, removing hard objects such as stones and branches, then constructing a herringbone slope (the herringbone slope with the gradient of 1:10 is constructed on the leveled field), a drainage channel and a water collecting tank, and paving an impermeable layer (composed of a layer of geotextile, a layer of HDPE film and a layer of geotextile) and a permeable liquid guide and drainage layer in the area; then, conveying the petroleum hydrocarbon polluted soil to be treated to a restoration site, and crushing and screening the oil-containing soil by using an ALLU screening hopper according to the soil quality condition of the oil-containing soil on site; then, under the condition of not damaging the impermeable layer, uniformly mixing the crushed and screened soil with a soil conditioner, a nutrient, a slow-release oxygen agent and a compound microbial agent by using small-sized excavating equipment, and then piling the mixture on the impermeable layer to improve the soil quality of the first layer of soil; and then, continuously piling, crushing and screening the oil-containing soil which is uniformly mixed with the soil property modifying agent, the nutrient, the slow-release oxygen agent and the compound microbial agent on the basis of the first layer of ploughed and homogenized oil-containing soil, so that the height of a biological pile is increased, and the soil property of the second layer of soil is modified.
In the period, the effective nitrogen and phosphorus content in the soil is detected by using a soil multi-parameter detector so as to meet the growth and propagation conditions of aerobic microorganisms and the degradation conditions of pollutants; maintaining certain soil looseness and water required by microbial metabolism activity, timely supplementing water by adopting a bacteria liquid/water automatic spraying system according to a regular water content detection result, and adding a proper amount of lime for adjustment when the pH value of the polluted soil is too low; when the pH value is too high, adding ammonium sulfate or aluminum sulfite for regulation; during the operation process, the rotary cultivator can turn over to ensure the uniform distribution of oxygen in the pile body, and the turning frequency is determined according to the oxygen content in the soil.
And sampling the biological piles every 25-35 days to detect the oil content, arranging sampling points as a detection unit on each pile, taking 3-5 soil points at each point for mixed detection, and when the earth volume of the pile is more than 1000m 3 When it is used, per 1000m 3 Sampling a sample, if the detection is qualified, finishing the treatment of the pile, and if the detection is not qualified, continuing to operate the treatment process until the detection is qualified.
Finally, after the soil is qualified through sampling detection of an effect evaluation unit, the soil meeting the restoration target limitation requirement can be used for foundation pit backfilling, roadbed bedding and the like.
In some preferred embodiments of the present invention, the spray system for spraying the compound microbial inoculum mainly comprises a water source, spray heads, a pipe network and a water pump, wherein the distance between the spray heads is 55% to 65% of the spray diameter (56%, 57%, 58%, 59%, 60%, 61%, 62%, 63% or 64% can be selected), so that the spray has good atomization effect and small water drops, the biological heap can be prevented from being washed away in the water replenishing process, and water can be saved.
The soil remediation agent and the method for remediating soil provided by the invention are used for remediating the soil polluted by petroleum hydrocarbon, and the soil polluted by the petroleum hydrocarbon can be remediated to the standard of construction land only in 20-60 days.
The principle of decomposing petroleum hydrocarbon by the composite microbial agent is as follows:
the microbial remediation of oil-containing soil utilizes the metabolism of microbes to degrade petroleum hydrocarbon in soil into harmless inorganic substances (CO) 2 、H 2 O) or other harmless substances. The order of the microbial degradability of the different hydrocarbons is as follows: linear alkanes less than C10>Linear alkanes of C10-C24 or longer>Branched alkanes less than C10>Branched alkanes of C10 to C24 or more>Monocyclic aromatic hydrocarbon>Polycyclic aromatic hydrocarbons>A heterocyclic aromatic hydrocarbon.
According to the chemical structure characteristics of hydrocarbons, the degradation route of the hydrocarbons mainly comprises two parts: alkane degradation pathways and aromatic degradation pathways.
(1) Degradation pathways for alkanes
The general straight-chain alkane substance is carried out according to the following biodegradation routes:
R-CH 2 -CH 3 →RCH 2 -CH 2 OH→RCH 2 -CHO→RCH 2 COOH → beta oxidation;
beta oxidation of alkanes can be hindered in certain environments, particularly branched alkanes, where omega oxidation can occur, i.e., microorganisms oxidize a methyl group at the end of the other end of the hydrocarbon chain when beta oxidation is hindered. Of course, ω oxidation also occurs in occasional cases simultaneously with β oxidation, i.e. at both ends of the alkane chain.
Under the action of microorganisms, alkanes can be oxidized into alkyl hydroperoxides, which are converted into fatty acids, and then degraded by beta oxidation. As follows:
CH 2 CH 3 →[R-CH 2 -CH 2 OOH]→RCH 2 -COOH → beta oxidation.
(2) Degradation pathway of aromatic hydrocarbons
Metabolic mechanism with aromatic hydrocarbons as the only carbon and energy source: the energy required for growth and reproduction by microbial degradation of organic matters is provided under the catalysis of various enzymes, and the microbial degradation of aromatic hydrocarbons is no exception. Under the induction of aromatic hydrocarbons and the like, the microorganisms can secrete monooxygenase and dioxygenase. Under the catalytic action of these enzymes, oxygen is added to the benzene ring to form C-O bond, and then the C-C bond is broken by hydrogenation, dehydration and other actions, so that the number of benzene rings is reduced. Wherein the fungus produces monooxygenase, an oxygen atom is added to the benzene ring to form an epoxide, and then H is added 2 O produces trans diols and phenols. Bacteria produce dioxygenases, which add two oxygen atoms to the benzene ring to form peroxides, which are then oxidized to cis-diols and dehydrogenated to produce phenols. Different pathways have different intermediates, but common intermediates are: catechol, 2, 5-dihydroxybenzoic acid, 3, 4-dihydroxy benzoic acid. Catechol is a common intermediate, with specific compounds being ortho, para or other depending on the position of the hydroxyl group. These metabolites are degraded via five similar pathways: ring carbon bond cleavage, succinic acid, fumaric acid, pyruvic acid, acetic acid or acetaldehyde. These substances can be used by microorganisms to synthesize cellular proteins, the final product being CO 2 And H 2 O。
Compared with the prior art, the invention has the beneficial effects that:
(1) the soil remediation agent provided by the invention can improve the remediation capability of microorganisms, shorten the remediation period, improve the remediation efficiency and greatly reduce the remediation cost.
(2) The composite microbial agent is adopted, and compared with a single microorganism, the composite microbial agent can efficiently decompose different kinds of pollutants in soil, so that a better repairing effect is obtained; in addition, the composite microbial agent obtained by separating and domesticating the specific soil can decompose different kinds of petroleum hydrocarbon in the soil more efficiently and comprehensively, so that a better remediation effect is obtained, the remediation period of the soil containing the petroleum hydrocarbon is shortened, and the remediation efficiency is improved.
(3) The invention can provide sufficient nutrition and a proper petroleum hydrocarbon decomposition environment for the growth of the indigenous bacteria by adding the soil property improving agent of a specific kind and the nutrient agent with a specific composition and adopting a biostimulation technology, so that the indigenous bacteria can decompose the petroleum hydrocarbon more efficiently.
(4) The slow-release oxygen technology adopted by the invention can reduce the plowing frequency and the process complexity of stack maintenance by adopting the specific type of slow-release oxygen agent, and simultaneously, the height of the stack can be stacked to be higher, thereby improving the treatment efficiency of microbial remediation and greatly reducing the remediation cost of soil.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is a schematic flow chart of a method for remediating soil according to an embodiment of the present invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings and the detailed description, but those skilled in the art will understand that the following described embodiments are some, not all, of the embodiments of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The compound microbial agents adopted in the following embodiments of the invention are all produced by Beijing Meiston science and technology development Limited company, and the type number of the compound microbial agents is MSTN-HT-004.
In addition, the soil to be restored in each of the following examples and comparative examples of the present invention is petroleum hydrocarbon contaminated soil from oil field of the eastern Ji province, and the amount of the soil is 100 parts.
Example 1
The soil remediation agent provided by the embodiment comprises the following components in parts by weight: 0.23 part of rice hull, 0.23 part of straw, 1 part of nutrient, 0.1 part of calcium peroxide and 0.5 part of compound microbial agent.
The nutrient comprises the following components in parts by weight: 15 parts of diatomite, 15 parts of cellulose, 10 parts of urea, 10 parts of monopotassium phosphate, 10 parts of calcium phosphate, 10 parts of dipotassium phosphate, 10 parts of calcium carbonate, 7 parts of anhydrous calcium chloride and 2 parts of magnesium sulfate.
Example 2
The soil remediation agent provided by the embodiment comprises the following components in parts by weight: 0.46 part of rice hull, 0.46 part of straw, 2 parts of nutrient, 0.2 part of calcium peroxide and 2 parts of compound microbial agent.
The nutrient comprises the following components in parts by weight: 20 parts of diatomite, 10 parts of cellulose, 15 parts of urea, 15 parts of monopotassium phosphate, 15 parts of calcium phosphate, 10 parts of dipotassium phosphate, 10 parts of calcium carbonate, 4 parts of anhydrous calcium chloride and 1 part of magnesium sulfate.
Example 3
The soil remediation agent provided by the embodiment comprises the following components in parts by weight: 0.7 part of rice hull, 0.7 part of straw, 3 parts of nutrient, 0.5 part of calcium peroxide and 3 parts of compound microbial agent.
The nutrient comprises the following components in parts by weight: 25 parts of diatomite, 5 parts of cellulose, 20 parts of urea, 15 parts of monopotassium phosphate, 20 parts of calcium phosphate, 15 parts of dipotassium phosphate, 8 parts of calcium carbonate, 2 parts of anhydrous calcium chloride and 1 part of magnesium sulfate.
Example 4
The method for restoring soil provided by the embodiment comprises the following steps:
(1) selecting an area with smooth ground and relatively high topography as a biological pile stacking area, measuring and laying lines to draw an accurate area of a biological pile stacking body, leveling the area, removing hard objects such as stones and branches, building a herringbone slope with a gradient of 1:10, a drainage channel and a water collecting tank on the leveled field, and laying an impermeable layer consisting of a layer of geotextile, a layer of HDPE (high density polyethylene film) and a layer of geotextile in the area.
(2) And conveying the petroleum hydrocarbon polluted soil to be restored to a restoration site, and crushing and screening the petroleum hydrocarbon polluted soil by using an ALLU screening hopper to obtain the petroleum hydrocarbon polluted soil with the particle size of less than 1.5 cm.
(3) Mixing the soil obtained in the step (2) with rice hulls and straws, uniformly stirring, spreading a nutrient and calcium peroxide, then spraying a compound microbial agent, and turning the soil by a rotary cultivator after the spraying is finished so as to fully and uniformly mix the soil;
secondly, piling the soil obtained in the step (3) on the impermeable layer by adopting small-sized excavating equipment under the condition of not damaging the impermeable layer, and carrying out piling treatment; wherein the stacking height is 50 cm.
(4) Mixing the soil obtained in the step (2) with rice hulls and straws, uniformly stirring, spreading a nutrient and calcium peroxide, then spraying a compound microbial agent, and turning the soil by a rotary cultivator after the spraying is finished so as to fully and uniformly mix the soil; and (4) piling the uniformly mixed soil on the soil obtained in the step (3), increasing the piling height to 100cm, and continuing to carry out piling treatment.
During the composting process in the step (3) and the step (4), monitoring the oxygen content, the carbon content, the available nitrogen content and the available phosphorus content in the soil, and monitoring the temperature, the pH value and the water content of the soil; controlling the ratio of the carbon content, the available nitrogen content and the available phosphorus content in the soil to be 100:10: 1; controlling the temperature of the soil to be 25-40 ℃, controlling the pH value to be 6.0-7.8 (when the pH value of the soil is too low, adding a proper amount of lime for adjustment, and when the pH value of the soil is too high, adding ammonium sulfate or aluminum sulfite for adjustment), and keeping the water content of the soil to be 25-35%; meanwhile, the oxygen in the pile body is uniformly distributed by turning, and the oxygen content in the soil is more than or equal to 7 percent by controlling the turning times.
(5) Sampling the pile body obtained in the step (4) every 30 days, detecting the oil content in the pile body, arranging sampling points on each pile body as a detection unit, taking 5 soil points at each point for mixed detection, and when the earth volume of the pile body is more than 1000m 3 When it is used, per 1000m 3 And sampling a sample, and if the sample is detected to be qualified, finishing the process of repairing the soil, and if the sample is not detected to be qualified, continuing repairing the soil until the sample is detected to be qualified.
The flow chart of the method for repairing soil provided by the embodiment is shown in fig. 1.
Comparative example 1
The composition of the soil remediation agent provided by the comparative example is basically the same as that of the soil remediation agent provided by the example 2, and the difference is only that 0.46 part of rice hulls and 0.46 part of straws in the example 2 are replaced by 0.92 part of diatomite.
Comparative example 2
The composition of the soil remediation agent provided by the comparative example is basically the same as that of example 2, except that 0.2 parts of calcium peroxide in example 2 is replaced by 0.2 parts of diatomite.
Comparative example 3
The composition of the soil remediation agent provided by the comparative example is basically the same as that of the soil remediation agent provided by the example 2, and the difference is only that 2 parts of the compound microbial agent in the example 2 is replaced by 2 parts of diatomite.
Comparative example 4
The composition of the soil remediation agent provided by the comparative example is basically the same as that of example 2, except that 2 parts of the nutrient in example 2 are replaced by 2 parts of diatomite.
Comparative example 5
The composition of the soil remediation agent provided by the comparative example is basically the same as that of example 2, and the difference is only that the compound microbial agent in example 2 is replaced by special oil removing bacteria produced by Guangzhou Yu Shali environmental protection technology Co.
Comparative example 6
The composition of the soil remediation agent provided by the comparative example is basically the same as that of example 2, and the difference is only that the nutrient in example 2 is replaced by SD-IV aerobic biological agent produced by Beijing shidou environmental technology Limited.
Experimental example 1
And detecting the content of petroleum hydrocarbon in the petroleum hydrocarbon polluted soil of the Jidong oil field before remediation. Meanwhile, the soil remediation agent prepared in each example and comparative example is used for remediating the petroleum hydrocarbon contaminated soil (the amount of the soil remediation agent is 100 parts) in the Jidong oil field by the method for remediating the soil in example 4, and the content of the petroleum hydrocarbon in each group of soil is detected after 60 days of remediation, and the results are respectively shown in the following table 1.
The method for detecting the content of each pollutant refers to gas chromatography HJ 1021-.
TABLE 1 content of petroleum hydrocarbons in the contaminated soil before remediation and in the soil after remediation for each group
As can be seen from Table 1 above, in each example, the addition amounts of the soil improver, the nutrient, the controlled-release oxygen agent, and the complex microbial agent of example 2 were optimized, and increasing or decreasing the addition amounts decreased the petroleum hydrocarbon decomposition efficiency.
Meanwhile, by comparing the repair results of example 2 with comparative examples 1, 2, 3, and 4, it can be seen that: the addition of the soil modifier, the nutrient, the slow-release oxygen agent and the compound microbial agent is all of great importance, and the replacement of any one of the materials can greatly reduce the decomposition efficiency of the petroleum hydrocarbon.
By comparing the repair results of example 2 with comparative examples 5 and 6, it can be seen that: compared with the commercially available microbial inoculum and nutritional agent, the compound microbial inoculum and nutritional agent of a specific kind used in the invention have higher petroleum hydrocarbon degradation efficiency.
Experimental example 2
The soil remediation agent of example 2 and the method of example 4 were used to remediate soil, respectively remediate the soil contaminated with petroleum hydrocarbon in Daqing oil field and the soil contaminated with petroleum hydrocarbon in Xinjiang Tuha oil field (30 days of remediation), and then the content of petroleum hydrocarbon in the soil before and after remediation was measured, and the results are shown in Table 2 below.
TABLE 2 remediation Effect of the soil remediation agent of example 2 on various contaminated soils
As can be seen from Table 2, the soil remediation agent of example 2 has good remediation effects on contaminated soil from different sources, and the remediation period is short, so that the content of petroleum hydrocarbon in the contaminated soil can be reduced to a low level only in 30 days.
While particular embodiments of the present invention have been illustrated and described, it will be appreciated that the above embodiments are merely illustrative of the technical solution of the present invention and are not restrictive; those of ordinary skill in the art will understand that: modifications may be made to the above-described embodiments, or equivalents may be substituted for some or all of the features thereof without departing from the spirit and scope of the present invention; the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention; it is therefore intended to cover in the appended claims all such alternatives and modifications that are within the scope of the invention.
Claims (15)
1. The soil repairing agent is characterized by comprising the following components in parts by weight:
0.4-1.5 parts of soil modifier, 0.5-3 parts of nutrient, 0.1-0.5 part of slow-release oxygen agent and 0.5-3 parts of compound microbial agent;
the soil modifier comprises rice hulls and straws;
the slow-release oxygen agent is calcium peroxide;
the compound microbial agent consists of bacillus subtilis, pseudomonas and bacillus licheniformis;
the compound microbial agent is a compound indigenous microbial agent, the type of the compound indigenous microbial agent is MSTN-HT-004, and the bacillus subtilis, the pseudomonas and the bacillus licheniformis in the compound microbial agent are obtained by separating and domesticating soil polluted by petroleum hydrocarbon;
the nutrient comprises the following components in parts by weight:
10-20 parts of nitrogenous fertilizer, 30-50 parts of phosphate fertilizer, 10-20 parts of secondary elements, 15-25 parts of diatomite and 5-15 parts of cellulose.
2. The soil remediation agent of claim 1 wherein said nitrogen fertilizer comprises urea.
3. The soil remediation agent of claim 1 wherein said phosphate fertilizer comprises at least one of potassium dihydrogen phosphate, calcium phosphate and dipotassium hydrogen phosphate.
4. The soil remediation agent of claim 1 wherein said secondary elements include at least one of calcium carbonate, calcium chloride and magnesium sulfate.
5. A method of remediating soil using the soil remediation agent of any one of claims 1 to 4, comprising the steps of:
the soil remediation agent is evenly mixed with the soil.
6. Method for remediating soil as claimed in claim 5, characterized in that it comprises in particular the steps of:
(a) uniformly mixing soil, a soil conditioner, a nutrient, a slow-release oxygen agent and a compound microbial agent, and composting;
(b) uniformly mixing soil, a soil conditioner, a nutrient, a slow-release oxygen agent and a compound microbial agent, placing the mixture on the surface of the soil obtained in the step (a), and continuously performing composting treatment;
(c) and (c) obtaining the repaired soil after the soil obtained in the step (b) is detected to be qualified.
7. The method for remediating soil as recited in claim 6, wherein in step (a) and/or step (b), the soil is subjected to a crushing and screening process.
8. The method for remediating soil as recited in claim 7, wherein the screened soil has a particle size of <1.5 cm.
9. The method for remediating soil as recited in claim 6, wherein in step (a), the height of the pile is 45-55 cm.
10. The method for remediating soil as recited in claim 6, wherein in step (b), the height of the pile is 90-110 cm.
11. The method for remediating soil as recited in claim 6, wherein in step (a) and/or step (b), the oxygen content, the carbon, nitrogen, and phosphorus content, and the temperature, pH, and water content of the soil are monitored.
12. The method for remediating soil as recited in claim 11, wherein the mass ratio of the carbon element to the nitrogen element to the phosphorus element in the soil is 90-110: 5-15: 1.
13. The method for remediating soil as recited in claim 11, wherein the soil has a temperature of 25-40 ℃, a pH of 6.0-7.8, and a water content of 25-35%.
14. The method for remediating soil as recited in claim 6, wherein in step (a) and/or step (b), the soil and components are mixed to homogeneity by at least one turn.
15. The method for remediating soil as recited in claim 14, wherein the number of plowing is controlled such that the oxygen content in the soil is 7% or more.
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