CN111822492B - Device system and method for treating petroleum polluted soil - Google Patents
Device system and method for treating petroleum polluted soil Download PDFInfo
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- CN111822492B CN111822492B CN202010754262.2A CN202010754262A CN111822492B CN 111822492 B CN111822492 B CN 111822492B CN 202010754262 A CN202010754262 A CN 202010754262A CN 111822492 B CN111822492 B CN 111822492B
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- 239000002689 soil Substances 0.000 title claims abstract description 373
- 238000000034 method Methods 0.000 title claims abstract description 78
- 239000003208 petroleum Substances 0.000 title claims description 41
- 238000002156 mixing Methods 0.000 claims abstract description 124
- 239000007787 solid Substances 0.000 claims abstract description 56
- 238000000926 separation method Methods 0.000 claims abstract description 49
- 238000012216 screening Methods 0.000 claims abstract description 42
- 238000002485 combustion reaction Methods 0.000 claims abstract description 34
- 238000005507 spraying Methods 0.000 claims abstract description 21
- 238000007664 blowing Methods 0.000 claims abstract description 13
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 98
- 239000007789 gas Substances 0.000 claims description 95
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 73
- 238000010926 purge Methods 0.000 claims description 56
- 239000003795 chemical substances by application Substances 0.000 claims description 54
- 239000002245 particle Substances 0.000 claims description 48
- 229960004887 ferric hydroxide Drugs 0.000 claims description 46
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims description 46
- 239000000243 solution Substances 0.000 claims description 45
- 239000000203 mixture Substances 0.000 claims description 44
- 238000010979 pH adjustment Methods 0.000 claims description 43
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 37
- 239000003546 flue gas Substances 0.000 claims description 37
- 239000007921 spray Substances 0.000 claims description 36
- 239000010902 straw Substances 0.000 claims description 36
- 239000000843 powder Substances 0.000 claims description 28
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 26
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 26
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 26
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 26
- 239000001099 ammonium carbonate Substances 0.000 claims description 26
- 239000004202 carbamide Substances 0.000 claims description 26
- 150000001875 compounds Chemical class 0.000 claims description 26
- 239000011259 mixed solution Substances 0.000 claims description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 17
- 239000003864 humus Substances 0.000 claims description 16
- 229920001661 Chitosan Polymers 0.000 claims description 14
- 239000010455 vermiculite Substances 0.000 claims description 14
- 229910052902 vermiculite Inorganic materials 0.000 claims description 14
- 235000019354 vermiculite Nutrition 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- 238000007873 sieving Methods 0.000 claims description 12
- -1 citric acid compound Chemical class 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 238000010408 sweeping Methods 0.000 claims description 10
- 238000000197 pyrolysis Methods 0.000 claims description 9
- 230000001105 regulatory effect Effects 0.000 claims description 9
- 238000005067 remediation Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 3
- 230000000536 complexating effect Effects 0.000 claims description 2
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 19
- 230000035558 fertility Effects 0.000 abstract description 4
- 235000015097 nutrients Nutrition 0.000 abstract description 4
- 239000013589 supplement Substances 0.000 abstract description 4
- 239000011133 lead Substances 0.000 description 29
- 239000003209 petroleum derivative Substances 0.000 description 29
- 239000011651 chromium Substances 0.000 description 19
- 229910052804 chromium Inorganic materials 0.000 description 10
- 239000000779 smoke Substances 0.000 description 10
- 241000209094 Oryza Species 0.000 description 9
- 235000007164 Oryza sativa Nutrition 0.000 description 9
- 238000004710 electron pair approximation Methods 0.000 description 9
- 238000002386 leaching Methods 0.000 description 9
- 229910052745 lead Inorganic materials 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 235000009566 rice Nutrition 0.000 description 9
- 240000008042 Zea mays Species 0.000 description 8
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 8
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 8
- 235000005822 corn Nutrition 0.000 description 8
- 241000209140 Triticum Species 0.000 description 6
- 235000021307 Triticum Nutrition 0.000 description 6
- 239000004568 cement Substances 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 235000017060 Arachis glabrata Nutrition 0.000 description 4
- 244000105624 Arachis hypogaea Species 0.000 description 4
- 235000010777 Arachis hypogaea Nutrition 0.000 description 4
- 235000018262 Arachis monticola Nutrition 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000035784 germination Effects 0.000 description 4
- 235000020232 peanut Nutrition 0.000 description 4
- 239000002957 persistent organic pollutant Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 230000008439 repair process Effects 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 235000021186 dishes Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000035508 accumulation Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000005445 natural material Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical class O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/02—Extraction using liquids, e.g. washing, leaching, flotation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/06—Reclamation of contaminated soil thermally
- B09C1/065—Reclamation of contaminated soil thermally by pyrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Inorganic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to a device system and a method for treating petroleum-polluted soil, wherein the device system for treating petroleum-polluted soil comprises a crushing device, a screening device, a first mixing device, a high-temperature air blowing device, a gas-solid separation device, a combustion device, a spraying device, a second mixing device and a third mixing device; the device system not only can treat the petroleum-polluted soil, but also can fully utilize organic matters in the petroleum-polluted soil; and the device system can also treat heavy metals in the soil, supplement nutrient elements lost in the soil and improve the fertility of the soil.
Description
Technical Field
The invention belongs to the technical field of environmental protection, relates to a soil treatment device and method, and particularly relates to a device system and method for treating soil polluted by soil.
Background
Soil is an important environmental basis for human beings, animals, plants and microorganisms to survive, and is an important place for the natural substances and energy to participate in the cycle processes of transformation, migration, accumulation and the like. However, with the development of modern civilization, soil problems are increasingly prominent.
After petroleum enters the soil, the petroleum can be adsorbed, decomposed, migrated or detained continuously through the physical, chemical and biological processes of the soil, so that the change of physical and chemical properties of the soil is caused, the physiological ecology of plants is influenced, the microbial community structure of the soil is changed, and meanwhile, environmental media such as atmosphere, water and the like can be influenced through the ways of volatilization, downward migration and the like, so that the health of human beings is threatened. The components of petroleum pollutants are very complex, especially the macromolecular substances such as aromatic hydrocarbon, colloid and asphaltene, and certain difficulty is brought to the restoration of petroleum polluted soil.
Currently, remediation methods for petroleum contaminated soil include bioremediation, leaching, and heat treatment methods. Bioremediation has the advantages of simple operation, low cost, small secondary pollution and the like, but can only treat low-concentration petroleum polluted soil, has long treatment period and can not effectively degrade heavy petroleum components such as colloid, asphaltene and the like; the leaching method has the defects that the leaching solution is difficult to separate from the soil, the viscous soil is difficult to adapt, and the leaching solution needs to be further treated. The heat treatment method has the remarkable advantages of high restoration efficiency, good adaptability to the types and concentration of organic pollutants in the soil and the like, and is widely applied to the petroleum polluted soil; however, the heat treatment method has the problems of high energy consumption, large influence on physical and chemical properties of soil, and the like. The pyrolysis process can pyrolyze heavy oil into volatizable and removed light oil and nonhazardous coke species at relatively low temperatures in an anaerobic or anoxic environment.
CN 107838187a discloses a method for repairing polycyclic aromatic hydrocarbon contaminated soil, comprising the following steps: (1) Eluting the polluted soil by using a chemical modified cyclodextrin eluent; (2) Preparing degradation bacteria, inoculating the prepared degradation bacteria into the eluted soil in the step (1) according to a preset proportion, and simultaneously adding biochar with preset quality into the eluted soil to obtain a mixture; (3) And (3) regulating the pH value of the mixture and the water content of the mixture in the step (2), and simultaneously carrying out light-shielding culture at a preset temperature to repair the polluted soil. However, as the method is a bioremediation method, the soil remediation treatment period is long, and only polycyclic aromatic hydrocarbon can be treated, so that heavy petroleum components such as colloid, asphalt and the like are difficult to effectively degrade.
CN 206981415U discloses an organic contaminated soil remediation system comprising a combustion furnace, a trench and a flue gas treatment unit; the groove is a through groove dug in the pollution area, one end of the groove is a smoke inlet and is connected with a smoke pipeline of the combustion furnace; the other end of the groove is connected with the flue gas treatment unit; specifically, the depth of the groove is 1-3.5m, the width is 0.5-1m, the length is 10-40m, and the other end of the groove is connected with the combustion furnace through a flue gas circulation pipeline; the flue gas treatment unit comprises a desulfurization device, a dust recovery device, a denitration device and leaching chemical treatment equipment which are sequentially connected. The organic contaminated soil restoration system is used for carrying out in-situ restoration on contaminated soil, but has lower restoration efficiency, and excessive smoke is needed in the restoration process, so that the burden of a subsequent smoke treatment unit is excessive.
CN 103936311a discloses a method for combining organic contaminated soil and urban exhaust gas treatment with a cement kiln, which comprises the following steps of RDF manufacture and cement kiln production process: and (3) delivering the RDF into a kiln tail decomposing furnace of the cement kiln, introducing tertiary air of the cement kiln, controlling the air quantity of the tertiary air to be 25-30% of that of the RDF when the RDF is fully combusted, and controlling the pyrolysis gasification temperature in the kiln tail decomposing furnace to be 650-750 ℃. The RDF is prepared by mixing and extruding urban waste, organic polluted soil and additives to form the RDF, controlling the water content of the RDF to be between 20 and 40 percent, and then sending the RDF into a cement kiln for pyrolysis and gasification; the weight portion ratio of the urban waste, the organic polluted soil and the additive is (10-70), 15-35 and 5-35. However, the urban waste has complex components, and is directly mixed with the organic polluted soil, so that the organic pollutants in the mixture are difficult to sufficiently remove.
Therefore, there is a need to provide a device system and a method for treating petroleum-polluted soil, so that the device system can fully utilize resources to treat organic pollutants in the soil, can repair the soil from which the organic pollutants are removed, and has higher repair efficiency.
Disclosure of Invention
The invention aims to provide a device system and a method for treating petroleum-polluted soil, wherein the device system can treat the petroleum-polluted soil so as to fully desorb organic matters in the soil; and meanwhile, the desorbed organic matters can be fully utilized. The method can effectively treat the petroleum-polluted soil, so that the soil meets the GB/T15618-1995 standard.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the invention provides a device system for treating petroleum-contaminated soil, which comprises a crushing device, a screening device, a first mixing device, a high-temperature gas purging device, a gas-solid separation device, a combustion device, a spraying device, a second mixing device and a third mixing device.
The crushing device and the screening device are sequentially connected with the first mixing device, and the first mixing device is used for mixing ferric hydroxide particles and/or ferrous oxide.
The discharge port of the first mixing device is connected with the top feed port of the high-temperature gas purging device; the high-temperature gas outlet of the combustion device is connected with the bottom gas inlet of the high-temperature gas blowing device; the top sweeping gas outlet of the high-temperature gas sweeping device is connected with the gas-solid separation device; the gas outlet of the gas-solid separation device is connected with the gas inlet of the combustion device; the solid outlet of the gas-solid separation device is connected with the first mixing device.
The soil outlet of the high-temperature gas purging device, the spraying device, the second mixing device and the third mixing device are sequentially connected; the second mixing device is used for adjusting the pH value of the sprayed soil; the third mixing device is used for mixing the soil with the soil restoration agent after the pH value is regulated.
Soil contaminated with petroleum is relatively viscous and difficult to mix with other additives. In this regard, the invention sets up breaker and screening plant before first mixing arrangement, will carry out broken screening to the soil contaminated by oil to the mix of soil and follow-up additive.
The soil mixed with ferric hydroxide particles and/or ferrous oxide in the first mixing device is in countercurrent contact with high-temperature gas in the high-temperature gas blowing device, wherein the high-temperature gas is smoke exhausted by the combustion device, and particularly the smoke with the temperature of 500-700 ℃. Due to the addition of ferric hydroxide particles and/or ferrous oxide, organic matters and heavy metals in the petroleum-polluted soil are fully desorbed, and the organic matters enter the gas-solid separation device along with the purge gas, so that solid particles carried by the purge gas are separated from the purge gas, and the influence of the carried solid particles on the normal operation of the combustion device is prevented.
Because the purge gas contains the organic matters which are desorbed and decomposed, the purge gas can be introduced into a combustion device for combustion, and the soil treated by the first mixing device is desorbed by utilizing the high temperature of the flue gas generated after combustion. The heavy metal is removed from the desorbed soil through spraying treatment, the pH value is regulated by a second mixing device, and then the soil is mixed with the soil restoration agent by a third mixing device, so that the soil can meet the GB/T15618-1995 standard. The device system not only can treat the petroleum-polluted soil, but also can fully utilize organic matters in the petroleum-polluted soil; and the device system can also treat heavy metals in the soil, supplement nutrient elements lost in the soil and improve the fertility of the soil.
Preferably, the crushing device is a soil crusher.
Preferably, the screening device is a soil screening machine having a screen mesh of 10-40 mesh, for example, 10 mesh, 12 mesh, 15 mesh, 16 mesh, 18 mesh, 20 mesh, 24 mesh, 25 mesh, 27 mesh, 28 mesh, 30 mesh, 32 mesh, 35 mesh, 36 mesh or 40 mesh, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the first mixing device, the second mixing device and the third mixing device are each independently drum mixers.
Preferably, the high temperature gas purging device is a fluidized bed purging device.
Preferably, the gas-solid separation device comprises a cyclone and/or a baghouse, preferably a cyclone.
The combustion apparatus of the present invention is conventional in the art, including but not limited to a burner, and can be suitably selected by one skilled in the art according to the process requirements.
The spraying device is a conventional spraying device in the field, and can be reasonably selected according to actual needs by a person skilled in the art, and the invention is not particularly limited.
Preferably, the first mixing device is provided with a jacket; purge gas discharged from a top purge gas outlet of the high-temperature gas purging device flows into the gas-solid separation device after passing through the jacket; or the gas flowing out from the gas-solid separation device flows into the combustion device after flowing through the jacket.
According to the invention, the purge gas flows into the gas-solid separation device after passing through the jacket, or the gas flowing out of the gas-solid separation device flows into the combustion device after passing through the jacket, so that the heat of the purge gas is fully utilized, the soil is preheated, and the purge effect of the high-temperature gas purge device is improved.
In a second aspect, the present invention provides a method of remediating petroleum contaminated soil using the apparatus system of the first aspect, the method comprising the steps of:
(1) Sequentially crushing and screening the petroleum polluted soil, and mixing the screened soil with ferric hydroxide particles and/or ferrous oxide to obtain a soil mixture;
(2) The soil mixture obtained in the step (1) is in countercurrent contact with the flue gas, and the purge gas is combusted after being subjected to gas-solid separation to generate the flue gas for countercurrent contact with the soil mixture; the purged soil is sequentially subjected to spray treatment and pH adjustment treatment and then is mixed with a soil restoration agent, so that the treatment of petroleum polluted soil is realized.
Preferably, the mass ratio of ferric hydroxide particles and/or ferrous oxide to the soil after sieving in the step (1) is 1 (20-40), for example, 1:20, 1:25, 1:30, 1:35 or 1:40, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
Preferably, the soil after the sieving in step (1) is mixed with ferric hydroxide colloidal particles and ferrous oxide.
According to the invention, through mixing the soil with the ferrous oxide, in the process of countercurrent contact between the soil and the flue gas, not only can organic components in the soil be desorbed, but also long-chain organic matters can be promoted to decompose, so that the organic components in the purge gas are more easy to burn. The addition of ferric hydroxide colloidal particles can strengthen the decomposition promoting effect of ferrous oxide, and is beneficial to the removal of heavy metals in the subsequent spraying process.
Preferably, the mass ratio of ferric hydroxide particles to ferrous oxide is 1 (3-5), for example, 1:3, 1:3.5, 1:4, 1:4.5 or 1:5, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
Preferably, the mesh size of the screen used in the step (1) is 10-40 mesh, for example, 10 mesh, 12 mesh, 15 mesh, 16 mesh, 18 mesh, 20 mesh, 24 mesh, 25 mesh, 27 mesh, 28 mesh, 30 mesh, 32 mesh, 35 mesh, 36 mesh or 40 mesh, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the flue gas temperature in step (2) is 500-700 ℃, for example 500 ℃, 550 ℃, 600 ℃, 650 ℃ or 700 ℃, but not limited to the values listed, and other values not listed in the range of values are equally applicable.
The invention uses the flue gas to desorb the organic matters in the soil, and the flow of the flue gas and the treatment capacity of the soil are not particularly limited. The flow of the smoke can be reasonably regulated according to the pollution degree of the soil by petroleum by a person skilled in the art, but the temperature of the smoke needs to be controlled to be 500-700 ℃, and the desorption of organic matters is not facilitated when the temperature of the smoke is too low, so that the organic matters cannot be fully desorbed in the countercurrent process of the soil and the smoke; the too high temperature of flue gas is unfavorable for the stable operation of the combustion device, increases the operation load of the combustion device, and can not promote the desorption effect of organic matters in soil.
Preferably, the spraying liquid used in the spraying treatment in the step (2) is Na 2 -a complexing solution of EDTA and citric acid.
Preferably, na in the compound solution 2 The EDTA concentration is 0.1 to 0.3mol/L, for example 0.1mol/L, 0.15mol/L, 0.2mol/L, 0.25mol/L or 0.3mol/L, but is not limited to the values recited, other values not recited in the numerical range being equally applicable.
Preferably, the concentration of the citric acid in the compound solution is 0.1-0.3mol/L, for example, 0.1mol/L, 0.15mol/L, 0.2mol/L, 0.25mol/L or 0.3mol/L, but the concentration is not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
The invention does not limit the dosage of the compound solution, and the end point of spraying is to ensure that the heavy metal content in the soil is not changed any more.
Preferably, the pH adjustment treatment in step (2) is pH adjustment using a mixed solution of ammonium bicarbonate and urea.
Preferably, the mass ratio of ammonium bicarbonate to urea in the mixed solution is (1-3): (1-3), for example, 1:1, 1:2, 1:3, 3:2 or 3:1, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, the pH of the soil after the pH adjustment treatment is from 6.5 to 7.5, for example, 6.5, 7 or 7.5, but is not limited to the values recited, and other values not recited in the range are equally applicable.
Preferably, the soil restoration agent comprises the following components in parts by weight:
the weight part of the straw powder in the soil restoration agent is 8-12 parts, for example, 8 parts, 9 parts, 10 parts, 11 parts or 12 parts, but is not limited to the listed values, and other non-listed values in the numerical range are applicable, preferably 10 parts.
The weight part of the natural humus in the soil restoration agent is 8-24 parts, for example, 8 parts, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, 20 parts, 22 parts or 24 parts, but the natural humus is not limited to the listed values, and other non-listed values in the numerical range are applicable, and the natural humus is preferably 16 parts.
The weight part of chitosan in the soil restoration agent is 4-8 parts, for example, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts or 8 parts, but is not limited to the recited values, and other non-recited values in the numerical range are equally applicable, preferably 6 parts.
The weight part of the biochar in the soil restoration agent is 25-45 parts, for example, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts, 36 parts, 38 parts, 40 parts, 42 parts or 45 parts, but is not limited to the recited values, and other non-recited values in the numerical range are equally applicable, preferably 35 parts.
Preferably, the preparation method of the biochar comprises the following steps: and (3) obtaining straws as raw materials, placing the raw materials into a tubular furnace at 450-550 ℃ under the protection of nitrogen for pyrolysis, wherein the pyrolysis time is 2-4h, and naturally cooling to room temperature to obtain the biochar.
Preferably, the straw comprises any one or a combination of at least two of rice straw, corn straw or peanut straw, and typical but non-limiting combinations include combinations of rice straw and corn straw, combinations of corn straw and peanut straw, combinations of rice straw and peanut straw, or combinations of rice straw, corn straw and peanut straw.
The pyrolysis temperature may be 450-550 ℃, for example, 450 ℃, 460 ℃, 470 ℃, 480 ℃, 490 ℃, 500 ℃, 510 ℃, 520 ℃, 530 ℃, 540 ℃ or 550 ℃, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable; the pyrolysis time is 2-4 hours, for example, 2, 2.5, 3, 3.5 or 4 hours, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The weight portion of vermiculite powder in the soil remediation agent is 2-5 parts, for example, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts or 5 parts, but is not limited to the recited values, and other non-recited values in the range of values are equally applicable, preferably 4 parts.
Preferably, the mass ratio of soil after the pH adjustment treatment in step (2) to soil remediation agent is 1 (0.1-0.6), and may be, for example, 1:0.1, 1:0.2, 1:0.3, 1:0.4, 1:0.5 or 1:0.6, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
As a preferred embodiment of the method according to the second aspect of the present invention, the method comprises the steps of:
(1) Crushing and screening the petroleum polluted soil in sequence, wherein the mesh number of the screen mesh used for screening is 10-40 meshes; mixing the sieved soil with ferric hydroxide particles and ferrous oxide to obtain a soil mixture; the mass ratio of the ferric hydroxide particles to the ferrous oxide to the soil after sieving is 1 (20-40); the mass ratio of the ferric hydroxide colloidal particles to the ferrous oxide is 1 (3-5);
(2) The soil mixture obtained in the step (1) is in countercurrent contact with the flue gas at the temperature of 500-700 ℃, and the purge gas is combusted after being subjected to gas-solid separation to generate the flue gas for countercurrent contact with the soil mixture; sequentially carrying out spray treatment and pH adjustment treatment on the purged soil, and then mixing with a soil restoration agent, thereby realizing the treatment of petroleum polluted soil;
the spray liquid used in the spray treatment in the step (2) is Na 2 -EDTA and citric acid compound solution, na in compound solution 2 The concentration of EDTA is 0.1-0.3mol/L, and the concentration of citric acid in the compound solution is 0.1-0.3mol/L;
the step (2) of pH adjustment is to adjust the pH by using a mixed solution of ammonium bicarbonate and urea, wherein the mass ratio of the ammonium bicarbonate to the urea in the mixed solution is (1-3), the pH value of the soil after the pH adjustment is 6.5-7.5;
the soil restoration agent comprises, by weight, 10 parts of straw powder, 16 parts of natural humus soil, 6 parts of chitosan, 35 parts of biochar and 4 parts of vermiculite powder; in the step (2), the mass ratio of the soil subjected to the pH adjustment treatment to the soil restoration agent is 1 (0.1-0.3).
Compared with the prior art, the invention has the following beneficial effects:
(1) The device system disclosed by the invention can treat the petroleum-polluted soil and fully utilize organic matters in the petroleum-polluted soil through the cooperation of the high-temperature gas blowing device and the combustion device; the device system can also treat heavy metals in the soil, supplement nutrient elements lost in the soil and improve the fertility of the soil;
(2) According to the invention, by mixing the soil with the ferrous oxide, the decomposition of long-chain organic matters can be promoted, so that the organic components in the purge gas are more easy to burn; the addition of ferric hydroxide colloidal particles can strengthen the decomposition promoting effect of ferrous oxide and is beneficial to the removal of heavy metals in the subsequent spraying process;
(3) The invention uses Na 2 The compound solution of EDTA and citric acid is used for leaching the soil, so that the leached soil can meet the GB/T15618-1995 standard, and the leaching solution has simple components and is convenient for subsequent pH adjustment treatment and addition of soil restoration agents.
Drawings
Fig. 1 is a schematic structural diagram of an apparatus system for treating petroleum-contaminated soil provided in example 1.
Wherein: 1, a crushing device; 2, screening device; 3, a first mixing device; 4, a high-temperature air blowing device; 5, a gas-solid separation device; 6, a combustion device; 7, a spraying device; 8, a second mixing device; 9, a third mixing device.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a device system for treating petroleum-polluted soil, the structural schematic diagram of which is shown in fig. 1, and the device system comprises a crushing device 1, a screening device 2, a first mixing device 3, a high-temperature gas purging device 4, a gas-solid separation device 5, a combustion device 6, a spraying device 7, a second mixing device 8 and a third mixing device 9;
The crushing device 1 and the screening device 2 are sequentially connected with the first mixing device 3, and the first mixing device 3 is used for mixing ferric hydroxide colloidal particles and ferrous oxide;
the discharge port of the first mixing device 3 is connected with the top feed port of the high-temperature gas purging device 4; the high-temperature gas outlet of the combustion device 6 is connected with the bottom gas inlet of the high-temperature gas blowing device 4; the top sweeping gas outlet of the high-temperature gas sweeping device 4 is connected with a gas-solid separation device 5; the gas outlet of the gas-solid separation device 5 is connected with the gas inlet of the combustion device 6; the solid outlet of the gas-solid separation device 5 is connected with the first mixing device 3;
the soil outlet of the high-temperature gas purging device 4, the spraying device 7, the second mixing device 8 and the third mixing device 9 are sequentially connected; the second mixing device 8 is used for adjusting the pH value of the sprayed soil; the third mixing device 9 is used for mixing the soil with the soil restoration agent after the pH value is regulated.
The crushing device 1 is a soil crusher; the screening device 2 is a soil screening machine, and the number of screen meshes is 10 meshes; the first mixing device 3, the second mixing device 8 and the third mixing device 9 are respectively and independently drum-type mixers; the high-temperature gas purging device 4 is a fluidized bed purging device; the gas-solid separation device 5 is a cyclone separator.
Example 2
The embodiment provides a device system for treating petroleum-polluted soil, which comprises a crushing device 1, a screening device 2, a first mixing device 3, a high-temperature air blowing device 4, a gas-solid separation device 5, a combustion device 6, a spraying device 7, a second mixing device 8 and a third mixing device 9;
the crushing device 1 and the screening device 2 are sequentially connected with the first mixing device 3, and the first mixing device 3 is used for mixing ferric hydroxide colloidal particles and ferrous oxide;
the discharge port of the first mixing device 3 is connected with the top feed port of the high-temperature gas purging device 4; the high-temperature gas outlet of the combustion device 6 is connected with the bottom gas inlet of the high-temperature gas blowing device 4; the top sweeping gas outlet of the high-temperature gas sweeping device 4 is connected with a gas-solid separation device 5; the gas outlet of the gas-solid separation device 5 is connected with the gas inlet of the combustion device 6; the solid outlet of the gas-solid separation device 5 is connected with the first mixing device 3;
the soil outlet of the high-temperature gas purging device 4, the spraying device 7, the second mixing device 8 and the third mixing device 9 are sequentially connected; the second mixing device 8 is used for adjusting the pH value of the sprayed soil; the third mixing device 9 is used for mixing the soil with the soil restoration agent after the pH value is regulated.
The crushing device 1 is a soil crusher; the screening device 2 is a soil screening machine, and the number of screen meshes is 20; the first mixing device 3, the second mixing device 8 and the third mixing device 9 are respectively and independently drum-type mixers; the high-temperature gas purging device 4 is a fluidized bed purging device; the gas-solid separation device 5 is a cyclone separator.
The first mixing device 3 is provided with a jacket; the purge gas discharged from the top purge gas outlet of the high temperature gas purge device 4 flows into the gas-solid separation device 5 after passing through the jacket.
Example 3
The embodiment provides a device system for treating petroleum-polluted soil, which comprises a crushing device 1, a screening device 2, a first mixing device 3, a high-temperature air blowing device 4, a gas-solid separation device 5, a combustion device 6, a spraying device 7, a second mixing device 8 and a third mixing device 9;
the crushing device 1 and the screening device 2 are sequentially connected with the first mixing device 3, and the first mixing device 3 is used for mixing ferric hydroxide colloidal particles and ferrous oxide;
the discharge port of the first mixing device 3 is connected with the top feed port of the high-temperature gas purging device 4; the high-temperature gas outlet of the combustion device 6 is connected with the bottom gas inlet of the high-temperature gas blowing device 4; the top sweeping gas outlet of the high-temperature gas sweeping device 4 is connected with a gas-solid separation device 5; the gas outlet of the gas-solid separation device 5 is connected with the gas inlet of the combustion device 6; the solid outlet of the gas-solid separation device 5 is connected with the first mixing device 3;
The soil outlet of the high-temperature gas purging device 4, the spraying device 7, the second mixing device 8 and the third mixing device 9 are sequentially connected; the second mixing device 8 is used for adjusting the pH value of the sprayed soil; the third mixing device 9 is used for mixing the soil with the soil restoration agent after the pH value is regulated.
The crushing device 1 is a soil crusher; the screening device 2 is a soil screening machine, and the mesh number of the screening device is 40 meshes; the first mixing device 3, the second mixing device 8 and the third mixing device 9 are respectively and independently drum-type mixers; the high-temperature gas purging device 4 is a fluidized bed purging device; the gas-solid separation device 5 is a cyclone separator.
The first mixing device 3 is provided with a jacket; the gas flowing out from the gas-solid separation device 5 flows through the jacket and then flows into the combustion device 6.
Application example 1
The application example provides a method for treating petroleum-polluted soil by applying the application example 1, wherein the initial content of total petroleum hydrocarbon in the treated simulated soil is 300mg/Kg, the initial content of Pb is 60mg/Kg, and the initial content of Cd is 1.5mg/Kg, and the method comprises the following steps:
(1) Crushing and screening the petroleum polluted soil in sequence; mixing the sieved soil with ferric hydroxide particles and ferrous oxide to obtain a soil mixture; the mass ratio of the ferric hydroxide particles to the ferrous oxide to the soil after sieving is 1:30; the mass ratio of the ferric hydroxide colloidal particles to the ferrous oxide is 1:4;
(2) The soil mixture obtained in the step (1) is in countercurrent contact with the flue gas at 600 ℃, and the purge gas is combusted after being subjected to gas-solid separation to generate the flue gas for countercurrent contact with the soil mixture; sequentially carrying out spray treatment and pH adjustment treatment on the purged soil, and then mixing with a soil restoration agent, thereby realizing the treatment of petroleum polluted soil;
the spray liquid used in the spray treatment in the step (2) is Na 2 -EDTA and citric acid compound solution, na in compound solution 2 The concentration of EDTA is 0.2mol/L, and the concentration of citric acid in the compound solution is 0.2mol/L;
the pH value adjusting treatment in the step (2) is to adjust the pH value by using a mixed solution of ammonium bicarbonate and urea, wherein the mass ratio of the ammonium bicarbonate to the urea in the mixed solution is 1:1, and the pH value of the soil after the pH value adjusting treatment is 7;
the soil restoration agent comprises, by weight, 10 parts of straw powder, 16 parts of natural humus soil, 6 parts of chitosan, 35 parts of biochar and 4 parts of vermiculite powder; and (3) the mass ratio of the soil subjected to the pH adjustment treatment in the step (2) to the soil restoration agent is 1:0.2.
The biochar is obtained by pyrolyzing rice straw in a tubular furnace at 500 ℃ under the protection of nitrogen for 3 hours and naturally cooling to room temperature.
The USA EPA Method 3550 Method is adopted to measure the total petroleum hydrocarbon removal rate in the treated soil, and the total petroleum hydrocarbon removal rate can reach 99.5%; and (3) measuring the Pb and Cr contents in the treated soil by using a hand-held soil heavy metal detector, wherein the Pb content is as low as 15.08mg/Kg, and the Cr content is as low as 0.24mg/Kg.
Application example 2
The application example provides a method for treating petroleum-polluted soil by applying the application example 1, wherein the initial content of total petroleum hydrocarbon in the treated simulated soil is 300mg/Kg, the initial content of Pb is 60mg/Kg, and the initial content of Cd is 1.5mg/Kg, and the method comprises the following steps:
(1) Crushing and screening the petroleum polluted soil in sequence; mixing the sieved soil with ferric hydroxide particles and ferrous oxide to obtain a soil mixture; the mass ratio of the ferric hydroxide particles to the ferrous oxide to the soil after sieving is 1:25; the mass ratio of the ferric hydroxide colloidal particles to the ferrous oxide is 1:3.5;
(2) The soil mixture obtained in the step (1) is in countercurrent contact with the flue gas at 550 ℃, and the purge gas is combusted after being subjected to gas-solid separation to generate the flue gas for countercurrent contact with the soil mixture; sequentially carrying out spray treatment and pH adjustment treatment on the purged soil, and then mixing with a soil restoration agent, thereby realizing the treatment of petroleum polluted soil;
The spray liquid used in the spray treatment in the step (2) is Na 2 -EDTA and citric acid compound solution, na in compound solution 2 The concentration of EDTA is 0.2mol/L, and the concentration of citric acid in the compound solution is 0.2mol/L;
the pH adjustment treatment in the step (2) is to adjust the pH by using a mixed solution of ammonium bicarbonate and urea, wherein the mass ratio of the ammonium bicarbonate to the urea in the mixed solution is 1:2, and the pH value of the soil after the pH adjustment treatment is 7;
the soil restoration agent comprises 9 parts of straw powder, 12 parts of natural humus soil, 7 parts of chitosan, 40 parts of biochar and 3 parts of vermiculite powder in parts by weight; and (3) the mass ratio of the soil subjected to the pH adjustment treatment in the step (2) to the soil restoration agent is 1:0.3.
The biochar is obtained by pyrolyzing corn straws in a tubular furnace at 480 ℃ under the protection of nitrogen for 3.5h and naturally cooling to room temperature.
The USA EPA Method 3550 Method is adopted to measure the total petroleum hydrocarbon removal rate in the treated soil, and the total petroleum hydrocarbon removal rate can reach 98.5%; and (3) measuring the Pb and Cr contents in the treated soil by using a hand-held soil heavy metal detector, wherein the Pb content is as low as 15.73mg/Kg, and the Cr content is as low as 0.27mg/Kg.
Application example 3
The application example provides a method for treating petroleum-polluted soil by applying the application example 1, wherein the initial content of total petroleum hydrocarbon in the treated simulated soil is 300mg/Kg, the initial content of Pb is 60mg/Kg, and the initial content of Cd is 1.5mg/Kg, and the method comprises the following steps:
(1) Crushing and screening the petroleum polluted soil in sequence; mixing the sieved soil with ferric hydroxide particles and ferrous oxide to obtain a soil mixture; the mass ratio of the ferric hydroxide particles to the ferrous oxide to the soil after sieving is 1:35; the mass ratio of the ferric hydroxide colloidal particles to the ferrous oxide is 1:4.5;
(2) The soil mixture obtained in the step (1) is in countercurrent contact with the flue gas at 650 ℃, and the purge gas is combusted after being subjected to gas-solid separation to generate the flue gas for countercurrent contact with the soil mixture; sequentially carrying out spray treatment and pH adjustment treatment on the purged soil, and then mixing with a soil restoration agent, thereby realizing the treatment of petroleum polluted soil;
the spray liquid used in the spray treatment in the step (2) is Na 2 -EDTA and citric acid compound solution, na in compound solution 2 The concentration of EDTA is 0.2mol/L, and the concentration of citric acid in the compound solution is 0.2mol/L;
the pH value adjusting treatment in the step (2) is to adjust the pH value by using a mixed solution of ammonium bicarbonate and urea, wherein the mass ratio of the ammonium bicarbonate to the urea in the mixed solution is 2:1, and the pH value of the soil after the pH value adjusting treatment is 7;
the soil restoration agent comprises, by weight, 8 parts of straw powder, 8 parts of natural humus soil, 8 parts of chitosan, 45 parts of biochar and 2 parts of vermiculite powder; and (3) the mass ratio of the soil subjected to the pH adjustment treatment in the step (2) to the soil restoration agent is 1:0.5.
The biochar is obtained by pyrolyzing corn stalks in a tubular furnace at 520 ℃ under the protection of nitrogen for 2.5h and naturally cooling to room temperature.
The USA EPA Method 3550 Method is adopted to measure the total petroleum hydrocarbon removal rate in the treated soil, and the total petroleum hydrocarbon removal rate can reach 97.4 percent; and (3) measuring the Pb and Cr contents in the treated soil by using a hand-held soil heavy metal detector, wherein the Pb content is as low as 15.28mg/Kg, and the Cr content is as low as 0.31mg/Kg.
Application example 4
The application example provides a method for treating petroleum-polluted soil by applying the application example 1, wherein the initial content of total petroleum hydrocarbon in the treated simulated soil is 300mg/Kg, the initial content of Pb is 60mg/Kg, and the initial content of Cd is 1.5mg/Kg, and the method comprises the following steps:
(1) Crushing and screening the petroleum polluted soil in sequence; mixing the sieved soil with ferric hydroxide particles and ferrous oxide to obtain a soil mixture; the mass ratio of the ferric hydroxide particles to the ferrous oxide to the soil after sieving is 1:20; the mass ratio of the ferric hydroxide colloidal particles to the ferrous oxide is 1:3;
(2) The soil mixture obtained in the step (1) is in countercurrent contact with the flue gas at 500 ℃, and the purge gas is combusted after being subjected to gas-solid separation to generate the flue gas for countercurrent contact with the soil mixture; sequentially carrying out spray treatment and pH adjustment treatment on the purged soil, and then mixing with a soil restoration agent, thereby realizing the treatment of petroleum polluted soil;
The spray liquid used in the spray treatment in the step (2) is Na 2 -EDTA and citric acid compound solution, na in compound solution 2 The concentration of EDTA is 0.3mol/L, and the concentration of citric acid in the compound solution is 0.3mol/L;
the pH adjustment treatment in the step (2) is to adjust the pH by using a mixed solution of ammonium bicarbonate and urea, wherein the mass ratio of the ammonium bicarbonate to the urea in the mixed solution is 3:1, and the pH value of the soil after the pH adjustment treatment is 6.5;
the soil restoration agent comprises, by weight, 11 parts of straw powder, 20 parts of natural humus soil, 5 parts of chitosan, 30 parts of biochar and 4 parts of vermiculite powder; and (3) the mass ratio of the soil subjected to the pH adjustment treatment in the step (2) to the soil restoration agent is 1:0.1.
The biochar is obtained by pyrolyzing corn stalks in a tube furnace at 450 ℃ under the protection of nitrogen for 4 hours and naturally cooling to room temperature.
The USA EPA Method 3550 Method is adopted to measure the total petroleum hydrocarbon removal rate in the treated soil, and the total petroleum hydrocarbon removal rate can reach 96.8%; and (3) measuring the Pb and Cr contents in the treated soil by using a hand-held soil heavy metal detector, wherein the Pb content is as low as 18.83mg/Kg, and the Cr content is as low as 0.29mg/Kg.
Application example 5
The application example provides a method for treating petroleum-polluted soil by applying the application example 1, wherein the initial content of total petroleum hydrocarbon in the treated simulated soil is 300mg/Kg, the initial content of Pb is 60mg/Kg, and the initial content of Cd is 1.5mg/Kg, and the method comprises the following steps:
(1) Crushing and screening the petroleum polluted soil in sequence; mixing the sieved soil with ferric hydroxide particles and ferrous oxide to obtain a soil mixture; the mass ratio of the ferric hydroxide particles to the ferrous oxide to the soil after sieving is 1:40; the mass ratio of the ferric hydroxide colloidal particles to the ferrous oxide is 1:5;
(2) The soil mixture obtained in the step (1) is in countercurrent contact with the flue gas at 700 ℃, and the purge gas is combusted after being subjected to gas-solid separation to generate the flue gas for countercurrent contact with the soil mixture; sequentially carrying out spray treatment and pH adjustment treatment on the purged soil, and then mixing with a soil restoration agent, thereby realizing the treatment of petroleum polluted soil;
the spray liquid used in the spray treatment in the step (2) is Na 2 -EDTA and citric acid compound solution, na in compound solution 2 The concentration of EDTA is 0.1mol/L, and the concentration of citric acid in the compound solution is 0.1mol/L;
the pH adjustment treatment in the step (2) is to adjust the pH by using a mixed solution of ammonium bicarbonate and urea, wherein the mass ratio of the ammonium bicarbonate to the urea in the mixed solution is 1:3, and the pH value of the soil after the pH adjustment treatment is 7.5;
the soil restoration agent comprises, by weight, 12 parts of straw powder, 24 parts of natural humus soil, 4 parts of chitosan, 25 parts of biochar and 5 parts of vermiculite powder; and (3) the mass ratio of the soil subjected to the pH adjustment treatment in the step (2) to the soil restoration agent is 1:0.6.
The biochar is obtained by pyrolyzing corn straw in a tubular furnace at 550 ℃ under the protection of nitrogen for 2 hours and naturally cooling to room temperature.
The USA EPA Method 3550 Method is adopted to measure the total petroleum hydrocarbon removal rate in the treated soil, and the total petroleum hydrocarbon removal rate can reach 96.1 percent; and (3) measuring the Pb and Cr contents in the treated soil by using a hand-held soil heavy metal detector, wherein the Pb content is as low as 18.49mg/Kg, and the Cr content is as low as 0.27mg/Kg.
Application example 6
The application example provides a method for treating petroleum-polluted soil by applying the application example 2, wherein the initial content of total petroleum hydrocarbon in the treated simulated soil is 300mg/Kg, the initial content of Pb is 60mg/Kg, and the initial content of Cd is 1.5mg/Kg, and the method comprises the following steps:
(1) Crushing and screening the petroleum polluted soil in sequence; mixing the sieved soil with ferric hydroxide particles and ferrous oxide to obtain a soil mixture; the mass ratio of the ferric hydroxide particles to the ferrous oxide to the soil after sieving is 1:30; the mass ratio of the ferric hydroxide colloidal particles to the ferrous oxide is 1:4;
(2) The soil mixture obtained in the step (1) is in countercurrent contact with the flue gas at 600 ℃, and the purge gas is combusted after being subjected to gas-solid separation to generate the flue gas for countercurrent contact with the soil mixture; sequentially carrying out spray treatment and pH adjustment treatment on the purged soil, and then mixing with a soil restoration agent, thereby realizing the treatment of petroleum polluted soil;
The spray liquid used in the spray treatment in the step (2) is Na 2 -EDTA and citric acid compound solution, na in compound solution 2 EDTA concentration of 0.2mol/L in the compounded solutionThe concentration of the citric acid is 0.2mol/L;
the pH value adjusting treatment in the step (2) is to adjust the pH value by using a mixed solution of ammonium bicarbonate and urea, wherein the mass ratio of the ammonium bicarbonate to the urea in the mixed solution is 1:1, and the pH value of the soil after the pH value adjusting treatment is 7;
the soil restoration agent comprises, by weight, 10 parts of straw powder, 16 parts of natural humus soil, 6 parts of chitosan, 35 parts of biochar and 4 parts of vermiculite powder; and (3) the mass ratio of the soil subjected to the pH adjustment treatment in the step (2) to the soil restoration agent is 1:0.2.
The biochar is obtained by pyrolyzing rice straw in a tubular furnace at 500 ℃ under the protection of nitrogen for 3 hours and naturally cooling to room temperature.
The USA EPA Method 3550 Method is adopted to measure the total petroleum hydrocarbon removal rate in the treated soil, and the total petroleum hydrocarbon removal rate can reach 98.6%; and (3) measuring the Pb and Cr contents in the treated soil by using a hand-held soil heavy metal detector, wherein the Pb content is as low as 15.44mg/Kg, and the Cr content is as low as 0.25mg/Kg.
Application example 7
The application example provides a method for treating petroleum-polluted soil by applying the application example 3, wherein the initial content of total petroleum hydrocarbon in the treated simulated soil is 300mg/Kg, the initial content of Pb is 60mg/Kg, and the initial content of Cd is 1.5mg/Kg, and the method comprises the following steps:
(1) Crushing and screening the petroleum polluted soil in sequence; mixing the sieved soil with ferric hydroxide particles and ferrous oxide to obtain a soil mixture; the mass ratio of the ferric hydroxide particles to the ferrous oxide to the soil after sieving is 1:30; the mass ratio of the ferric hydroxide colloidal particles to the ferrous oxide is 1:4;
(2) The soil mixture obtained in the step (1) is in countercurrent contact with the flue gas at 600 ℃, and the purge gas is combusted after being subjected to gas-solid separation to generate the flue gas for countercurrent contact with the soil mixture; sequentially carrying out spray treatment and pH adjustment treatment on the purged soil, and then mixing with a soil restoration agent, thereby realizing the treatment of petroleum polluted soil;
step (2) sprayingThe spray liquid used for treatment is Na 2 -EDTA and citric acid compound solution, na in compound solution 2 The concentration of EDTA is 0.2mol/L, and the concentration of citric acid in the compound solution is 0.2mol/L;
the pH value adjusting treatment in the step (2) is to adjust the pH value by using a mixed solution of ammonium bicarbonate and urea, wherein the mass ratio of the ammonium bicarbonate to the urea in the mixed solution is 1:1, and the pH value of the soil after the pH value adjusting treatment is 7;
the soil restoration agent comprises, by weight, 10 parts of straw powder, 16 parts of natural humus soil, 6 parts of chitosan, 35 parts of biochar and 4 parts of vermiculite powder; and (3) the mass ratio of the soil subjected to the pH adjustment treatment in the step (2) to the soil restoration agent is 1:0.2.
The biochar is obtained by pyrolyzing rice straw in a tubular furnace at 500 ℃ under the protection of nitrogen for 3 hours and naturally cooling to room temperature.
The USA EPA Method 3550 Method is adopted to measure the total petroleum hydrocarbon removal rate in the treated soil, and the total petroleum hydrocarbon removal rate can reach 98.8%; and (3) measuring the Pb and Cr contents in the treated soil by using a hand-held soil heavy metal detector, wherein the Pb content is as low as 15.27mg/Kg, and the Cr content is as low as 0.23mg/Kg.
Application example 8
The application example provides a method for treating petroleum-polluted soil by applying the application example 1, wherein the initial content of total petroleum hydrocarbon in the treated simulated soil is 300mg/Kg, the initial content of Pb is 60mg/Kg, and the initial content of Cd is 1.5mg/Kg, and the method comprises the following steps:
(1) Crushing and screening the petroleum polluted soil in sequence; mixing the sieved soil with ferric hydroxide colloidal particles to obtain a soil mixture; the mass ratio of the ferric hydroxide colloidal particles to the sieved soil is 1:30;
(2) The soil mixture obtained in the step (1) is in countercurrent contact with the flue gas at 600 ℃, and the purge gas is combusted after being subjected to gas-solid separation to generate the flue gas for countercurrent contact with the soil mixture; sequentially carrying out spray treatment and pH adjustment treatment on the purged soil, and then mixing with a soil restoration agent, thereby realizing the treatment of petroleum polluted soil;
The spray liquid used in the spray treatment in the step (2) is Na 2 -EDTA and citric acid compound solution, na in compound solution 2 The concentration of EDTA is 0.2mol/L, and the concentration of citric acid in the compound solution is 0.2mol/L;
the pH value adjusting treatment in the step (2) is to adjust the pH value by using a mixed solution of ammonium bicarbonate and urea, wherein the mass ratio of the ammonium bicarbonate to the urea in the mixed solution is 1:1, and the pH value of the soil after the pH value adjusting treatment is 7;
the soil restoration agent comprises, by weight, 10 parts of straw powder, 16 parts of natural humus soil, 6 parts of chitosan, 35 parts of biochar and 4 parts of vermiculite powder; and (3) the mass ratio of the soil subjected to the pH adjustment treatment in the step (2) to the soil restoration agent is 1:0.2.
The biochar is obtained by pyrolyzing rice straw in a tubular furnace at 500 ℃ under the protection of nitrogen for 3 hours and naturally cooling to room temperature.
The USA EPA Method 3550 Method is adopted to measure the total petroleum hydrocarbon removal rate in the treated soil, and the total petroleum hydrocarbon removal rate can reach 90.7%; and (3) measuring the Pb and Cr contents in the treated soil by using a hand-held soil heavy metal detector, wherein the Pb content is 31.29mg/Kg at the minimum and the Cr content is 0.52mg/Kg at the minimum.
Application example 9
The application example provides a method for treating petroleum-polluted soil by applying the application example 1, wherein the initial content of total petroleum hydrocarbon in the treated simulated soil is 300mg/Kg, the initial content of Pb is 60mg/Kg, and the initial content of Cd is 1.5mg/Kg, and the method comprises the following steps:
(1) Crushing and screening the petroleum polluted soil in sequence; mixing the sieved soil with ferrous oxide to obtain a soil mixture; the mass ratio of the ferrous oxide to the sieved soil is 1:30;
(2) The soil mixture obtained in the step (1) is in countercurrent contact with the flue gas at 600 ℃, and the purge gas is combusted after being subjected to gas-solid separation to generate the flue gas for countercurrent contact with the soil mixture; sequentially carrying out spray treatment and pH adjustment treatment on the purged soil, and then mixing with a soil restoration agent, thereby realizing the treatment of petroleum polluted soil;
the spray liquid used in the spray treatment in the step (2) is Na 2 -EDTA and citric acid compound solution, na in compound solution 2 The concentration of EDTA is 0.2mol/L, and the concentration of citric acid in the compound solution is 0.2mol/L;
the pH value adjusting treatment in the step (2) is to adjust the pH value by using a mixed solution of ammonium bicarbonate and urea, wherein the mass ratio of the ammonium bicarbonate to the urea in the mixed solution is 1:1, and the pH value of the soil after the pH value adjusting treatment is 7;
The soil restoration agent comprises, by weight, 10 parts of straw powder, 16 parts of natural humus soil, 6 parts of chitosan, 35 parts of biochar and 4 parts of vermiculite powder; and (3) the mass ratio of the soil subjected to the pH adjustment treatment in the step (2) to the soil restoration agent is 1:0.2.
The biochar is obtained by pyrolyzing rice straw in a tubular furnace at 500 ℃ under the protection of nitrogen for 3 hours and naturally cooling to room temperature.
The USA EPA Method 3550 Method is adopted to measure the total petroleum hydrocarbon removal rate in the treated soil, and the total petroleum hydrocarbon removal rate can reach 93.5%; and (3) measuring the Pb and Cr contents in the treated soil by using a hand-held soil heavy metal detector, wherein the Pb content is as low as 27.64mg/Kg, and the Cr content is as low as 0.43mg/Kg.
Wheat germination rates in the treated soil, the uncontaminated simulated soil (without petroleum hydrocarbon, lead and chromium added) and the contaminated soil (the initial content of total petroleum hydrocarbon is 300mg/Kg, the initial content of Pb is 60mg/Kg, and the initial content of Cd is 1.5 mg/Kg) provided in application examples 1-9 were tested, and the full and healthy wheat seeds 1100 were selected and randomly divided into 11 groups of 100 grains each, and uniformly scattered in 11 glass culture dishes containing the same quality soil. Placing 11 culture dishes in a climatic chamber, keeping the soil water holding rate at 60%, regulating the sunlight duration of the incubator to 16h, setting the daytime temperature at 26 ℃, setting the nighttime temperature at 22 ℃ and the air humidity at 70%, observing the germination condition of the wheat, knowing that no wheat is germinated, and measuring the germination rate of the wheat, wherein the result is shown in table 1.
TABLE 1
| Wheat germination percentage (%) | |
| Application example 1 | 81 |
| Application example 2 | 79 |
| Application example 3 | 72 |
| Application example 4 | 75 |
| Application example 5 | 76 |
| Application example 6 | 78 |
| Application example 7 | 77 |
| Application example 8 | 51 |
| Application example 9 | 58 |
| Simulated soil free of contamination by contaminants | 65 |
| Contaminated soil | 4 |
In summary, the device system disclosed by the invention can treat the petroleum-polluted soil and fully utilize organic matters in the petroleum-polluted soil through the cooperation of the high-temperature gas blowing device and the combustion device; the device system can also treat heavy metals in the soil, supplement nutrient elements lost in the soil and improve the fertility of the soil; according to the invention, by mixing the soil with the ferrous oxide, the decomposition of long-chain organic matters can be promoted, so that the organic components in the purge gas are more easy to burn; the addition of ferric hydroxide colloidal particles can strengthen the decomposition promoting effect of ferrous oxide and is beneficial to the removal of heavy metals in the subsequent spraying process; the invention uses Na 2 The compound solution of EDTA and citric acid is used for leaching the soil, so that the leached soil can meet the GB/T15618-1995 standard, and the leaching solution has simple components and is convenient for subsequent pH adjustment treatment and addition of soil restoration agents.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.
Claims (20)
1. A method of remediating petroleum contaminated soil, said method comprising the steps of:
(1) Crushing and screening the petroleum polluted soil in sequence, and mixing the screened soil with ferric hydroxide particles and ferrous oxide to obtain a soil mixture;
the mass ratio of the ferric hydroxide colloidal particles to the ferrous oxide is 1 (3-5);
(2) The soil mixture obtained in the step (1) is in countercurrent contact with the flue gas, and the purge gas is combusted after being subjected to gas-solid separation to generate the flue gas for countercurrent contact with the soil mixture; sequentially carrying out spray treatment and pH adjustment treatment on the purged soil, and then mixing with a soil restoration agent, thereby realizing the treatment of petroleum polluted soil;
the soil remediation agent comprises the following components in parts by weight: 8-12 parts of straw powder, 8-24 parts of natural humus soil, 4-8 parts of chitosan, 25-45 parts of biochar and 2-5 parts of vermiculite powder;
the preparation method of the biochar comprises the following steps: straw is obtained as a raw material, the raw material is placed in a tubular furnace at 450-550 ℃ under the protection of nitrogen for pyrolysis, the pyrolysis time is 2-4h, and the biochar is obtained after natural cooling to room temperature;
the preparation method is carried out in a device system for treating petroleum-polluted soil, and the device system for treating petroleum-polluted soil comprises a crushing device, a screening device, a first mixing device, a high-temperature air blowing device, a gas-solid separation device, a combustion device, a spraying device, a second mixing device and a third mixing device;
The crushing device and the screening device are sequentially connected with a first mixing device, and the first mixing device is used for mixing and screening the soil, ferric hydroxide colloidal particles and ferrous oxide;
the discharge port of the first mixing device is connected with the top feed port of the high-temperature gas purging device; the high-temperature gas outlet of the combustion device is connected with the bottom gas inlet of the high-temperature gas blowing device; the top sweeping gas outlet of the high-temperature gas sweeping device is connected with the gas-solid separation device; the gas outlet of the gas-solid separation device is connected with the gas inlet of the combustion device; the solid outlet of the gas-solid separation device is connected with the first mixing device;
the soil outlet of the high-temperature gas purging device, the spraying device, the second mixing device and the third mixing device are sequentially connected; the second mixing device is used for adjusting the pH value of the sprayed soil; the third mixing device is used for mixing the soil with the soil restoration agent after the pH value is regulated.
2. The method of claim 1, wherein the crushing device is a soil crusher.
3. The method of claim 1, wherein the screening device is a soil screening machine having a screen mesh of 10-40 mesh.
4. The method of claim 1, wherein the first mixing device, the second mixing device, and the third mixing device are each independently drum agitators.
5. The method of claim 1, wherein the high temperature gas purge device is a fluidized bed purge device.
6. The method according to claim 1, wherein the gas-solid separation device comprises a cyclone and/or a baghouse.
7. The method according to claim 4, wherein the first mixing device is provided with a jacket;
purge gas discharged from a top purge gas outlet of the high-temperature gas purging device flows into the gas-solid separation device after passing through the jacket; or the gas flowing out from the gas-solid separation device flows into the combustion device after flowing through the jacket.
8. The method according to claim 1, wherein the mass ratio of ferric hydroxide particles and ferrous oxide to the soil after sieving in step (1) is 1 (20-40).
9. The method of claim 1, wherein the mesh size of the screen used in the screening of step (1) is 10-40 mesh.
10. The method of claim 1, wherein the flue gas of step (2) has a temperature of 500-700 ℃.
11. The method according to claim 1, wherein the spray liquid used in the spray treatment in the step (2) is Na 2 -a complexing solution of EDTA and citric acid.
12. The method of claim 11, wherein Na in the compounded solution 2 The concentration of EDTA is 0.1-0.3mol/L.
13. The method of claim 11, wherein the concentration of citric acid in the compounded solution is 0.1-0.3mol/L.
14. The method of claim 1, wherein the pH adjustment in step (2) is performed using a mixed solution of ammonium bicarbonate and urea.
15. The method of claim 14, wherein the mass ratio of ammonium bicarbonate to urea in the mixed solution is (1-3): 1-3.
16. The method according to claim 1, wherein the pH of the soil after the pH treatment is adjusted to a pH of 6.5-7.5.
17. The method according to claim 1, wherein the mass ratio of the soil after the pH adjustment treatment in the step (2) to the soil restoration agent is 1 (0.1-0.6).
18. The method of claim 1, wherein the soil remediation agent comprises, in parts by weight:
10 parts of straw powder
16 parts of natural humus soil
Chitosan 6 parts
35 parts of biochar
4 parts of vermiculite powder.
19. The method according to claim 17, wherein the mass ratio of the soil after the pH adjustment treatment in the step (2) to the soil restoration agent is 1 (0.1-0.3).
20. The method according to claim 1, characterized in that it comprises the steps of:
(1) Crushing and screening the petroleum polluted soil in sequence, wherein the mesh number of the screen mesh used for screening is 10-40 meshes; mixing the sieved soil with ferric hydroxide particles and ferrous oxide to obtain a soil mixture; the mass ratio of the ferric hydroxide particles to the ferrous oxide to the soil after sieving is 1 (20-40); the mass ratio of the ferric hydroxide colloidal particles to the ferrous oxide is 1 (3-5);
(2) The soil mixture obtained in the step (1) is in countercurrent contact with the flue gas at the temperature of 500-700 ℃, and the purge gas is combusted after being subjected to gas-solid separation to generate the flue gas for countercurrent contact with the soil mixture; sequentially carrying out spray treatment and pH adjustment treatment on the purged soil, and then mixing with a soil restoration agent, thereby realizing the treatment of petroleum polluted soil;
the spray liquid used in the spray treatment in the step (2) is Na 2 -EDTA and citric acid compound solution, na in compound solution 2 The concentration of EDTA is 0.1-0.3mol/L, and the concentration of citric acid in the compound solution is 0.1-0.3mol/L;
the step (2) of pH adjustment is to adjust the pH by using a mixed solution of ammonium bicarbonate and urea, wherein the mass ratio of the ammonium bicarbonate to the urea in the mixed solution is (1-3), the pH value of the soil after the pH adjustment is 6.5-7.5;
the soil restoration agent comprises, by weight, 10 parts of straw powder, 16 parts of natural humus soil, 6 parts of chitosan, 35 parts of biochar and 4 parts of vermiculite powder; in the step (2), the mass ratio of the soil subjected to the pH adjustment treatment to the soil restoration agent is 1 (0.1-0.3).
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