CN103664261A - Method for treating phthalic acid esters (PAEs) in agricultural wastes - Google Patents
Method for treating phthalic acid esters (PAEs) in agricultural wastes Download PDFInfo
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- CN103664261A CN103664261A CN201310680762.6A CN201310680762A CN103664261A CN 103664261 A CN103664261 A CN 103664261A CN 201310680762 A CN201310680762 A CN 201310680762A CN 103664261 A CN103664261 A CN 103664261A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention discloses a method for treating PAEs in agricultural wastes. The method comprises the following steps: grinding plant residue containing the PAEs; mixing the ground plant residue and animal dung containing the PAEs at the mass ratio of 1:(1-10), adding water after mixing, regulating the mass content of the water to 55-65 percent to form a uniformly mixed composting body and placing the composting body in a closed container or a sealed composting site, and composting for 10-50 d till completing the composting to form clinker. The method is relatively simple to operate, suitable for relatively wide places, relatively low in treating cost, and not only can be adopted in a special closed container, but also can be implemented in site in the field, and not only is the minimization of the PAEs in the agricultural wastes realized, but also the composted clinker can be used for agricultural production directly and safely, so that double benefits are achieved, and the method has important practical significance and economic values.
Description
Technical field
The present invention relates to environmental organic pollutant Ecological Disposal technical field, particularly a kind of method of administering phthalic ester in agricultural wastes.
Background technology
Phthalic ester (phthalic acid esters, be called for short PAEs) by a rigid plane aromatic hydrocarbons and two plastic non-linear aliphatic side chainses, formed, conventionally by the esterification between anhydride phthalic acid and various alcohols, obtain, in agricultural wastes (as crop residues and fowl and animal excrement etc.), also extensively exist.
PAEs is extensively present in water body, soil and air.That along with PAEs is a large amount of, produces and products thereof is widely used, and a large amount of town sewage and rubbish is discharged into farmland, and PAEs has become one of modal organic pollutant in agricultural land soil.Due to the estrogen effect of PAEs, and teratogenesis, carcinogenic and mutagenic characteristic, PAEs forms serious threat to ecotope, food safety and HUMAN HEALTH.U.S. EPA is (being DMP, DEP, DBP, BBP, DEHP and DOP) using 6 kinds of PAEs as priority pollutants.Er China Environment Priority is controlled in pollutent, also has 3 kinds of PAEs compounds (being dimethyl phthalate (DMP), diethyl phthalate (DEP), dinoctyl phthalate (DOP)) strictly to control.
Plant can absorb by root system, accumulate PAEs from soil, also can absorb airborne PAEs by blade, causes the PAEs accumulation in crop residues; In fowl and animal excrement, also contain higher PAEs.Crop residues, fowl and animal excrement are the sources of main organic substance in agricultural planting industry, and when these agricultural waste that contain PAEs are used as fertilizer, if it is not administered in advance, PAEs will get back in environment again, and human health is threatened.
Compost is that to utilize various organic waste (crop straw, weeds, leaf, peat, rubbish and other waste etc.) be main raw material, mixes the organic fertilizer that people and animals' fecaluria forms through composting decomposition.Mainly utilize the effect of multiple-microorganism, by plant Organic residues, carry out mineral, humify and innoxious, the Nutrient Transformation that makes the organic of various complexity is soluble nutrient and soil ulmin.Through research and development for many years, composting technology is more ripe, but in decomposed manure, still retains the PAEs of high level.It is reported, through in the garbage compost of thermophilic fermentation, the content of dibutyl phthalate, dimixo-octyl phthalate reaches respectively 10g/t and 20g/t, and in the garbage compost naturally becoming thoroughly decomposed, phthalic acid ester content is 4.27～9.98g/t.
PAEs in physical environment can degrade by approach such as physical action, ozone oxidation, ultraviolet photolysis, but biological degradation is the main path of PAEs mineralising in environment circle.In recent years, the biological degradation of PAEs is subject to extensive concern, and obtains some progress.In carrying out water body, soil, PAEs biological degradation is studied, biological degradation (Chang et al., 2007 of also having carried out the PAEs in the PAEs biological degradation in domestic waste, sludge of sewage treatment plant; Marttinen et al., 2004; Zheng Xiaoying etc., 2006) research.But these degradation method complicated operations, also must carry out in specific place, and restricted condition is more, and degraded cost is higher, and meanwhile, the grog producing after degraded can not reuse, and the improvement of physical environment is still existed to larger pressure.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of method of administering phthalic ester in agricultural wastes is provided, the method is simple to operate, and the grog that heap postpone produces can also recycle.
Technical scheme of the present invention is: a kind of method of administering phthalic ester in agricultural wastes, comprises the following steps:
(1) plant residue that contains PAEs is pulverized;
(2) plant residue after pulverizing is mixed with the fowl and animal excrement that contains PAEs, the mass ratio of plant residue and fowl and animal excrement is 1:1～10, adds water during mixing, and to regulate the mass content of water be 55%～65%, the heap body that formation mixes;
(3) heap body is placed in to the compost place of encloses container or sealing, the 10～50d that banks up, until compost completes, forms grog.
Wherein, while regulating the mass content of water, can test by manual compression, now pile body and should feel moister, and have the situation of infiltration, but be also unlikely to present a large amount of water droplets.Heap body is banked up in process, can be by manually maintaining the micro-aerobic condition of heap body.
In described step (2), when plant residue mixes with fowl and animal excrement, add urea to regulate the carbon-nitrogen ratio in heap body, the carbon-nitrogen ratio C/N after mixing in heap body is 10～30:1.
In described step (3), in the heap body process of banking up, at interval of 5～10d, manually stir heap body, can improve heap body aerobic environment, the decomposition that makes to pile body is more even.
In described step (3), in the process that heap body is banked up, adopt air pump, by aeration head, heap body is carried out to air blast, be conducive to microbiological deterioration.
In aforesaid method, after compost completes, can take out grog and be directly used in agriculture production.PAEs in plant residue and fowl and animal excrement is degraded by multiple-microorganism in composting process, is converted into soluble nutrient and soil ulmin together with other complicated organism.
Described PAEs is DMP(dimethyl phthalate), DEP(diethyl phthalate), DBP(dibutyl phthalate) or DEHP(dimixo-octyl phthalate) in one or more.
As a kind of preferred version, described plant residue is soybean stalk, and fowl and animal excrement is chicken manure, and the mass ratio of chicken manure and soybean stalk is 2:1.
As a kind of preferred version, described plant residue is rice straw, and fowl and animal excrement is chicken manure, and the mass ratio of chicken manure and rice straw is 2:1.
As a kind of preferred version, described plant residue is melon vine leaf, and fowl and animal excrement is pig manure, and the mass ratio of melon vine leaf and pig manure is 1:1, and melon vine leaf adds nitrogen content while mixing with pig manure be 40% urea, and the carbon-nitrogen ratio C/N after mixing in heap body is 10:1.
As a kind of preferred version, described plant residue is melon vine leaf, and fowl and animal excrement is pig manure, and the mass ratio of melon vine leaf and pig manure is 1:1, and melon vine leaf adds nitrogen content while mixing with pig manure be 40% urea, and the carbon-nitrogen ratio C/N after mixing in heap body is 20:1.
As a kind of preferred version, described plant residue is melon vine leaf, and fowl and animal excrement is pig manure, and the mass ratio of melon vine leaf and pig manure is 1.05:10, and the carbon-nitrogen ratio C/N after mixing in heap body is 30:1.
The present invention, with respect to prior art, has following beneficial effect:
In this improvement agricultural wastes, the method for phthalic ester is compared with traditional treatment method, and its operation is simpler, and applicable situation is wider, and processing cost is also lower.In this improvement agricultural wastes, the method for phthalic ester is by adopting crop straw, fowl and animal excrement to mix, by composting mode, administer residual PAEs in agricultural waste, the agricultural wastes that polluted by PAEs are carried out to compost treatment, simple to operate, not only can in special-purpose encloses container, carry out, also can implement on the spot in field, not only realize the minimizing of PAEs in agricultural waste, and the grog after composting can also be directly used in agriculture production safely, kill two birds with one stone, have important practical significance and economic worth.
Accompanying drawing explanation
Fig. 1 is the content schematic diagram of each pollutent in embodiment 1.
Fig. 2 is the content schematic diagram of each pollutent in embodiment 2.
Fig. 3 is 4 content schematic diagram of piling DMP in bodies of embodiment 3.
Fig. 4 is 4 content schematic diagram of piling DEP in bodies of embodiment 3.
Fig. 5 is 4 content schematic diagram of piling DBP in bodies of embodiment 3.
Fig. 6 is 4 content schematic diagram of piling DEHP in bodies of embodiment 3.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1
A kind of method of administering phthalic ester in agricultural wastes of the present embodiment, adopts soybean stalk and chicken manure as raw material, comprises the following steps:
(1) soybean stalk that contains PAEs is pulverized;
(2) soybean stalk after pulverizing is mixed with the chicken manure that contains PAEs, the mass ratio of chicken manure and soybean stalk is 2:1, adds water during mixing, and to regulate the mass content of water be 55%～65%, the heap body that formation mixes, and each piles the about 0.03m of body
3, the carbon-nitrogen ratio C/N after mixing in heap body is 25:1; In this process, while regulating the mass content of water, can test by manual compression, now pile body and should feel moister, and have the situation of infiltration, but be also unlikely to present a large amount of water droplets;
(3) heap body is placed in growth cabinet and is carried out, the test period of banking up is 10 days, and a few days ago Temperature Setting is 35 ℃, is set as afterwards 40 ℃; Bank up in process, connect aeration head heap body is carried out to air blast with air pump, be conducive to microbiological deterioration, blast volume is 0.1L/(min basin), each 30min, every day 2 times.
The content of DMP, DEHP in 1d, 5d, 10d sampling analysis heap body, test-results as shown in Figure 1.DMP in heap body, DEHP content are along with the increase of the time of banking up has decline in various degree.When 1d, DMP content 3.95mg/kg, DEHP content 3.68mg/kg, during to 10d, DMP content drops to 2.55mg/kg, and DEHP content drops to 1.41mg/kg.The 10d that banks up, DMP clearance be 35.4%, DEHP clearance higher than DMP, be 61.7%.The method of this evidence compost has degradation effect to the DMP in agricultural wastes, DEHP.
Embodiment 2
A kind of method of administering phthalic ester in agricultural wastes of the present embodiment, adopts rice straw and chicken manure as raw material, comprises the following steps:
(1) rice straw that contains PAEs is pulverized;
(2) rice straw after pulverizing is mixed with the chicken manure that contains PAEs, the mass ratio of chicken manure and soybean stalk is 2:1, adds water during mixing, and to regulate the mass content of water be 55%～65%, the heap body that formation mixes, and each piles the about 0.03m of body
3, the carbon-nitrogen ratio C/N after mixing in heap body is 25:1; In this process, while regulating the mass content of water, can test by manual compression, now pile body and should feel moister, and have the situation of infiltration, but be also unlikely to present a large amount of water droplets;
(3) heap body is placed in growth cabinet and is carried out, the test period of banking up is 10 days, and a few days ago Temperature Setting is 35 ℃, is set as afterwards 40 ℃; Bank up in process, connect aeration head heap body is carried out to air blast with air pump, be conducive to microbiological deterioration, blast volume is 0.1L/(min basin), each 30min, every day 2 times.
The content of DMP, DEHP in 1d, 5d, 10d sampling analysis heap body, test-results as shown in Figure 2.DMP in heap body, DEHP content are along with the increase of the time of banking up also has decline in various degree.When 1d, DMP content 3.08mg/kg, DEHP content 2.49mg/kg, during to 10d, DMP content drops to 0.25mg/kg, and DEHP content drops to 2.13mg/kg.The 10d that banks up, DMP clearance is to be 14.5% up to 91.9%, DEHP clearance.The method of this evidence compost has degradation effect to the DMP in agricultural wastes, DEHP.
Embodiment 3
A kind of method of administering phthalic ester in agricultural wastes of the present embodiment, adopts melon vine leaf and pig manure as raw material, in field, tests, and by 4 heap bodies, tests relatively simultaneously, and 4 heap bodies respectively arrange 2 parallel processing heap bodies and test.In 4 heap bodies, the proportioning of each raw material is as shown in the table:
4 heap bodies are all processed by the following method:
(1) take melon vine leaf, pig manure, urea and the water of corresponding weight, be stacked in watt cylinder in field after mixing, closed cylinder mouth, starts compost; The mass content that regulates water in mixing process is 55%～65%, while regulating the mass content of water, can test by manual compression, now piles body and should feel moister, and have the situation of infiltration, but be also unlikely to present a large amount of water droplets;
(2) every 5d opens the closed cylinder mouth of each heap body, manually will pile body and fully mix once (maybe heap body being poured out to turning once), thereby improve the aerobic environment (being supplemental oxygen) of piling body, promotes microbiological deterioration, until compost is ripe.
In above-mentioned treating processes, the content of DMP, DEP, DBP, DEHP in 1d, 15d, 30d, each heap body of 45d sampling analysis respectively.Test-results is as shown in Fig. 3～6.Wherein:
As shown in Figure 3,4 heap bodies DMP content when 1d is 0.979～1.175mg/kg to the content situation of 1, respectively piling DMP in body, after compost 45d, drops to 0.018～0.095mg/kg.In 4 heap bodies, the content of DMP is along with there is decline in various degree the compost time.The degradation effect of wherein piling body 2 and heap body 3 is best, and when 15d, clearance reaches respectively 74.5% and reach respectively 98.2% and 98.2% during 80.2%, the 45d; In heap body 1, the degradation speed of DMP is slightly slow, but when 45d, clearance is also up to 90.7%; The degraded situation of heap body 4 is compared poor, and during 45d, clearance is 41.0%.As can be seen here, improve the degradation rate that C/N can improve compost DMP.
As shown in Figure 4,4 heap bodies DEP content when 1d is 0.008～0.502mg/kg to the content situation of 2, respectively piling DEP in body, after compost 45d, drops to 0～0.128mg/kg.Heap body 1, heap body 2 and heap body 3 are along with the prolongation of time, and DEP content has decline in various degree, when 45d, the clearance of heap body 2 reaches 100%, and the clearance of heap body 3 and heap body 1 is up to 93.2% and 80.1%, and heap body 4 is when 15d, DEP content goes up not down, and starts subsequently to reduce.As can be seen here, improve the degradation capability that C/N can improve compost DEP.
As shown in Figure 5,4 heap bodies DBP content when 1d is 5.546～12.099mg/kg to the content situation of 3, respectively piling DBP in body, after compost 45d, drops to 0.101～0.385mg/kg.4 heap bodies DBP is had to extraordinary removal effect, when when 15d, clearance has reached the 81.5%～94.5%, the 45d up to 95.7%～99.2%.
As shown in Figure 6,4 heap bodies DEHP content when 1d is 0.437～0.750mg/kg to the content situation of 4, respectively piling DEHP in body, after compost 45d, all drops to 0mg/kg.4 heap bodies have good removal effect to DEHP, and when when 15d, clearance has reached the 25.6%～75.7%, the 45d, the DEHP clearance of 4 heap bodies is all up to 100%.
The content (being the total content of DMP, DEP, DBP and DEHP) of PAEs in 4 heap bodies is arranged as shown in the table:
As seen from the above table, the total amount of 4 heap body PAEs when 1d is 69.756～111.579mg, after compost 45d, and remaining 2.133～4.706mg.4 heap bodies have good removal effect to PAEs, and during 15d, clearance just reaches 70.0%～89.6%, and the total removal amount of PAEs up to 93.8%～97.8%, 4 heap bodies during to 45d reaches 65.449～108.566mg.
From the present embodiment, in this improvement agricultural wastes, the method for phthalic ester all has good degradation effect to the DMP in agricultural wastes, DEP, DBP, DEHP.
As mentioned above, just can realize preferably the present invention, above-described embodiment is only preferred embodiment of the present invention, is not used for limiting practical range of the present invention; Be that all equalizations of doing according to content of the present invention change and modify, all by the claims in the present invention scope required for protection, contained.
Claims (10)
1. a method of administering phthalic ester in agricultural wastes, is characterized in that, comprises the following steps:
(1) plant residue that contains PAEs is pulverized;
(2) plant residue after pulverizing is mixed with the fowl and animal excrement that contains PAEs, the mass ratio of plant residue and fowl and animal excrement is 1:1～10, adds water during mixing, and to regulate the mass content of water be 55%～65%, the heap body that formation mixes;
(3) heap body is placed in to the compost place of encloses container or sealing, the 10～50d that banks up, until compost completes, forms grog.
2. a kind of method of administering phthalic ester in agricultural wastes according to claim 1, it is characterized in that, in described step (2), when plant residue mixes with fowl and animal excrement, add urea to regulate the carbon-nitrogen ratio in heap body, the carbon-nitrogen ratio C/N after mixing in heap body is 10～30:1.
3. a kind of method of administering phthalic ester in agricultural wastes according to claim 1, is characterized in that, in described step (3), in the process that heap body is banked up, at interval of 5～10d, manually stirs heap body.
4. a kind of method of administering phthalic ester in agricultural wastes according to claim 1, is characterized in that, in described step (3), in the process that heap body is banked up, adopts air pump, by aeration head, heap body is carried out to air blast.
5. a kind of method of administering phthalic ester in agricultural wastes according to claim 1, is characterized in that, described PAEs is one or more in DMP, DEP, DBP or DEHP.
6. a kind of method of administering phthalic ester in agricultural wastes according to claim 1, is characterized in that, described plant residue is soybean stalk, and fowl and animal excrement is chicken manure, and the mass ratio of chicken manure and soybean stalk is 2:1.
7. a kind of method of administering phthalic ester in agricultural wastes according to claim 1, is characterized in that, described plant residue is rice straw, and fowl and animal excrement is chicken manure, and the mass ratio of chicken manure and rice straw is 2:1.
8. a kind of method of administering phthalic ester in agricultural wastes according to claim 2, it is characterized in that, described plant residue is melon vine leaf, fowl and animal excrement is pig manure, the mass ratio of melon vine leaf and pig manure is 1:1, melon vine leaf adds nitrogen content while mixing with pig manure be 40% urea, and the carbon-nitrogen ratio C/N after mixing in heap body is 10:1.
9. a kind of method of administering phthalic ester in agricultural wastes according to claim 2, it is characterized in that, described plant residue is melon vine leaf, fowl and animal excrement is pig manure, the mass ratio of melon vine leaf and pig manure is 1:1, melon vine leaf adds nitrogen content while mixing with pig manure be 40% urea, and the carbon-nitrogen ratio C/N after mixing in heap body is 20:1.
10. a kind of method of administering phthalic ester in agricultural wastes according to claim 2, it is characterized in that, described plant residue is melon vine leaf, and fowl and animal excrement is pig manure, the mass ratio of melon vine leaf and pig manure is 1.05:10, and the carbon-nitrogen ratio C/N after mixing in heap body is 30:1.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104087517A (en) * | 2014-07-03 | 2014-10-08 | 环境保护部华南环境科学研究所 | Fungus capable of degrading phthalic acid ester and pesticide simultaneously and application thereof |
| CN106478311A (en) * | 2016-12-27 | 2017-03-08 | 贵州大学 | A kind of fertilizer for phthalic acid ester contaminated soil |
| CN110252787A (en) * | 2019-05-20 | 2019-09-20 | 上海市农业科学院 | Application of the earthworm excrement in degradation DEHP |
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| CN102795900A (en) * | 2012-08-29 | 2012-11-28 | 攀枝花市西宇生物科技有限公司 | Method for preparing bio-organic fertilizer by utilizing eupatorium adenophorum |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102795900A (en) * | 2012-08-29 | 2012-11-28 | 攀枝花市西宇生物科技有限公司 | Method for preparing bio-organic fertilizer by utilizing eupatorium adenophorum |
Non-Patent Citations (2)
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| 莫测辉等: "城市污泥中有机污染物的研究进展", 《农业环境保护》 * |
| 蔡全英等: "城市污泥与稻草堆肥中邻苯二甲酸酯（PAEs）的研究", 《应用生态学报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104087517A (en) * | 2014-07-03 | 2014-10-08 | 环境保护部华南环境科学研究所 | Fungus capable of degrading phthalic acid ester and pesticide simultaneously and application thereof |
| CN106478311A (en) * | 2016-12-27 | 2017-03-08 | 贵州大学 | A kind of fertilizer for phthalic acid ester contaminated soil |
| CN110252787A (en) * | 2019-05-20 | 2019-09-20 | 上海市农业科学院 | Application of the earthworm excrement in degradation DEHP |
| CN110252787B (en) * | 2019-05-20 | 2021-07-20 | 上海市农业科学院 | Application of earthworm cast in DEHP degradation |
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Application publication date: 20140326 |