CN103624072A - Radio-frequency heating vapor-extraction advanced-oxidation in-situ restoration apparatus suitable for high-viscosity contaminated soil and restoration method thereof - Google Patents

Abstract

The invention discloses a radio-frequency heating vapor-extraction advanced-oxidation in-situ restoration apparatus suitable for high-viscosity contaminated soil and a restoration method thereof. The apparatus comprises multiple heating extractors and injection pipes; each heating extractor comprises an extraction pipe and a heating pipe; a radio-frequency electrode is arranged in the heating pipe and is connected with an adapter and a radio-frequency launcher; the outer shell of the extraction pipe is provided with a hole; the inner wall of the extraction pipe is provided with grids; the upper parts of all of the extraction pipes are connected together and connected with a condensation unit, a gas-liquid separator and a vacuum pump in sequence. The restoration method comprises: arranging the multiple heating extractors and the injection pipes, and keeping the distance between per two heating extractors at 2-5 m; respectively injecting calcium carbonate powder with an addition amount of 10%-15% and a sodium persulfate solution with an addition amount 20%-25% into the contaminated soil; and performing intermittent extraction with a heating temperature of 100-500 DEG C and a heating time of 100-140 h. According to the technical scheme, the restoration effect on the high-viscosity contaminated soil is obvious in a short time, the pollutant removing rate is high, the heating is rapid, the restoration time is short and the restoration efficiency is high.

Description

Be applicable to radio frequency heating gas phase extracting advanced oxidation in-situ repairing device and the restorative procedure thereof of high viscosity contaminated soil

Technical field

The invention belongs to contaminated soil recovery technique field, relate to a kind of radio frequency heating gas phase extracting advanced oxidation in-situ repairing device and restorative procedure and repair materials that is applicable to volatility and semi-volatile organic matter high viscosity contaminated soil.

Background technology

The features such as in high viscosity soil, volatile organic matter and semi-volatile organic matter have long half time, absorption affinity is strong and difficult, there are the polluting property and the harmfulness that are different from other pollutants, are listed in the toxic pollutant that potentially danger in environment is large, should preferentially control.This pollutant can threaten underground water source water quality safety, contaminated air, change soil characteristic, harm the crops, meanwhile, the hydrocarbon gas accumulate in building is underground may be explosion caused, and make with leak the public land that hydrocarbon compound contacts under pipe network facilities accelerated ageing.

Although China not yet puts into effect corresponding standard and statute VOCs-contaminated Soils is controlled, but in the domestic flourishing city of the minorities such as Shanghai, the harm problem of volatile organic matter has caused the great attention of government department, and how disposing rationally and effectively organic material contaminated soil has become the technical barrier of needing solution badly.

Summary of the invention

The object of the invention is to: a kind of radio frequency heating gas phase extracting advanced oxidation in-situ repairing device and restorative procedure that is applicable to volatility and semi-volatile organic matter high viscosity contaminated soil is provided, and to solve, remediation efficiency in the processing procedure of volatility and semi-volatile organic matter high viscosity contaminated soil in prior art is low, the technical problem of length consuming time.

Technical scheme of the present invention is as follows:

A radio frequency heating gas phase extracting advanced oxidation in-situ repairing device that is applicable to high viscosity contaminated soil, it comprises one or more injection-tubes, and is arranged in injection-tube a plurality of heating extractors around; Each heating extractor comprise extraction tube and be located at the heating tube in extraction tube, radio-frequency electrode is placed in heating tube, radio-frequency electrode is connected with adaptation by coaxial cable, adaptation is connected with radiofrequency launcher by coaxial cable; On extraction tube shell, there are a plurality of perforates; In extraction tube, filler and catalyst are equipped with in heating tube outside; Extraction tube inwall is provided with one deck width of mesh than filler and the little grid of catalyst particle size; The extracting tube connector on all extraction tubes top links together, and is sequentially connected with condensing unit, gas-liquid separator, vavuum pump.

Can be rounded, oval between injection-tube and heating extractor, the arranged distribution mode of polygon or other form; Circular arranged distribution mode (be injection-tube at center, a plurality of heating extraction devices are distributed on circumference); More preferably (heat extractor has seven to regular hexagon arranged distribution mode, is distributed on orthohexagonal six points and central point; Injection-tube has six, is distributed in six leg-of-mutton centers that form after regular hexagon diagonal angle line).

Above-mentioned heating extractor is a kind of volatile organic matter prosthetic appliance that integrates radio frequency heating, two kinds of functions of negative pressure extraction, and the power of radio frequency heating can customize according to the difference of field condition.

A radio frequency heating gas phase extracting advanced oxidation in-situ remediation method that is applicable to high viscosity contaminated soil that uses above-mentioned prosthetic device, it comprises the steps:

(1) according to contaminated soil place concrete condition, a plurality of heating extractors and injection-tube are arranged in reparation place (circular or regular hexagon arranged distribution mode), and the spacing between a plurality of heating extractors is 2～5 meters (fixed according to place concrete condition);

(2) the extracting tube connector of all heating extractors is linked together, be merged into a shared tube connector, then this shared tube connector is sequentially connected with condensing unit, gas-liquid separator and vavuum pump;

(3) calcium carbonate powder after grinding is directly injected in high viscosity contaminated soil by injection-tube, adding proportion issoil quality 10%～15%;

(4) the sodium peroxydisulfate solution that is 30% by mass concentration is directly injected in high viscosity contaminated soil by injection-tube, and adding proportion is soil quality 20%～25%;

(5) the first preheated one-section time, then in heating, open vavuum pump and carry out extracting, adopting intermittently extracting mode, the temperature of controlling heating source is 100～500 ℃, 100～140 hours heat times; Under negative pressure state, by the vapours extracting, through condensing unit, gas-liquid separator, finally enter in tail gas treatment device and process.

Preferred version: in said method, intermittently extracting mode is: every extracting is after 12 hours, and take out for 12 hours again at interval; The temperature of controlling heating source is 200 ℃; 120 hours heat times; Can be to carrying out the recovery of organic phase from gas-liquid separator condensate liquid out.

Beneficial effect of the present invention:

The present invention's employing is injected at the compound repair materials by calcium carbonate powder and sodium peroxydisulfate solution composition around heating/extraction well, activated the oxidation susceptibility of compound repair materials, strengthen the degraded of semi-volatile organic matter, meanwhile improved the good diffusion of composite repairing material in soil media.Repair materials A calcium carbonate powder is first injected in soil by injection-tube, absorbs the moisture in soil, is convenient to the transmission of follow-up repair materials B sodium peroxydisulfate solution in soil.The present invention is obvious to high viscosity contaminated soil repairing effect at short notice, and pollutants removal rate is high.

The present invention adopts radio frequency heating, and its advantage is heating rapidly, and repair time is short, and remediation efficiency is high.Traditional Resistant heating principle is that resistance wire itself produces high temperature, then heat high-temperature region, center from heating source is slowly transmitted to the appearance low-temperature space of heating source again, speed is slow, and the actual temperature and the appearance temperature that are positioned at heating source center have larger error, although resistance wire stops heating when heating-up temperature reaches requirement, owing to there being temperature error, heating source still continues to soil conduction heat, cause temperature to be controlled inaccurate, affected remediation efficiency; And the operation principle of radio frequency heating system is high-frequency induction, heated object is the current heating by self, heat energy is to produce by heating object is whole, temperature is controlled in real time accurately, heating source internal and external temperature is consistent, obviously improved remediation efficiency, the shortcoming such as repair time of having overcome traditional resistor silk heating technique is long, efficiency is low.

Accompanying drawing explanation

The plan structure schematic diagram of Fig. 1 radio frequency heating gas phase of the present invention extracting advanced oxidation in-situ repairing device, that is the arranged distribution figure of heating extractor and injection-tube;

Injection-tube in Fig. 2 in-situ repairing device of the present invention and the schematic diagram of heating extractor in underground pollution soil;

The master of the heating extractor in Fig. 3 the present invention looks cross-sectional view;

The external view of the extraction tube in Fig. 4 the present invention.

In figure: 1,heating tube 2,radiofrequency launcher 3,adaptation 4, coaxial cable

5, radio-frequency electrode 6, extraction tube 7, extraction tube shell perforate 8, extracting tube connector

9, the perforate onheating extractor 10, injection-tube 11, injection-tube tube wall

12, filler andcatalyst 13, grid

The specific embodiment

Below in conjunction with the drawings and specific embodiments, the invention will be further described.

Embodiment 1:

As shown in Fig. 1-4, a kind of radio frequency heating gas phase extracting advanced oxidation in-situ repairing device that is applicable to high viscosity contaminated soil of the present invention, it comprises by the injection-tube of arranged inregular hexagon shape 10 and heating extractor 9(heating extractor 9 seven, is distributed on orthohexagonal six points and central point; Injection-tube 10 has six, is distributed in six leg-of-mutton centers that form after regular hexagon diagonal angle line); Each heating extractor comprisesextraction tube 6 and is located at theheating tube 1 in extraction tube, and radio-frequency electrode 5 is placed inheating tube 1, and radio-frequency electrode is connected withadaptation 3 bycoaxial cable 4, andadaptation 3 passes throughcoaxial cable 4 and is connected withradiofrequency launcher 2; On extraction tube shell, there are a plurality of perforates (being extraction tube shell perforate 7); Filler andcatalyst 12 are equipped with in the interior heating tube of extraction tube 61 outside; Extraction tube inwall is provided with one deck width of mesh than filler and thelittle grid 13 of catalyst particle size; The extractingtube connector 8 on all extraction tubes top links together, and is sequentially connected with condensing unit, gas-liquid separator, vavuum pump.Injection-tube tube wall is provided with perforate (being the perforate 11 on injection-tube tube wall).

Embodiment 2:

" a kind of radio frequency heating gas phase extracting advanced oxidation in-situ repairing device that is applicable to high viscosity contaminated soil " application in repairing Cao Lu town chemical plant volatility and semi-volatile organic matter pollution high viscosity soil in the present invention

Be positioned at Shanghai Pudong New Area Cao Luzhen Cao Luji, to the east of road high up in the air, reach golden sea route in the south, to Pudong canal, Bei Zhidongjing road (seeing Fig. 2-1).

Investigation finds to have chemical plant, Yi Geyuangu road in base range.Plot, chemical plant is " L " type, and thing is about 160m, the widest about 105m in east, and the widest about 69m in western part, floor space is about 13445m².Contaminated area is about 4513 square metres.

Restorative procedure is as follows:

(1) according to contaminated soil place concrete condition, a plurality of heating extractors and injection-tube are distributed in and are repaired in place by circular arrangement, the spacing between a plurality of heating extractors is 2～5 meters;

(2) the extracting tube connector of all heating extractors is linked together, be merged into a shared tube connector, then this shared tube connector is sequentially connected with condensing unit, gas-liquid separator and vavuum pump;

(3) calcium carbonate powder after grinding is directly injected in high viscosity contaminated soil by injection-tube, adding proportion is soil quality 12.5%;

(4) the sodium peroxydisulfate solution that is 30% by the mass concentration being mixed with by deionized water is directly injected in high viscosity contaminated soil by injection-tube, and adding proportion is soil quality 22.5%;

(5) the first preheated one-section time, then in heating, open vavuum pump and carry out extracting, adopting intermittently extracting mode, the temperature of controlling heating source (being heating tube) is 200 ℃, 120 hours heat times; Under negative pressure state, by the vapours extracting, through condensing unit, gas-liquid separator, finally enter in tail gas treatment device and process.

Repair materials A calcium carbonate powder is injected in soil by injection-tube, absorbs the moisture in soil, is convenient to the transmission of follow-up repair materials B sodium peroxydisulfate solution in soil.Be accompanied by heat and negative pressure extraction that heating extractor discharges, half volatile and volatile organic matter in soil are fully degraded.

In case, the project of pedotheque analysis is mainly semi-volatile organic matter (two (2-ethylhexyl) phthalate ester, carbazole, azobenzene and N-nitroso di-n-propylamine) and volatile organic matter (chloroform, benzene, 1,2-dichloroethanes and 1,2,3-trichloropropane).The analytical standard adopting in analytic process, instrument title, instrument model etc. are as shown in table 1.Soil pollutant content after reparation is in Table 2.

Table 1 pedotheque analytical parameters, method and instrument

Test name	Method	Instrument title	Instrument model
				Semi-volatile organic matter	USEPA8270D-2007	Chromatography of gases-GC-MS	6890/5973N
Volatile organic matter	USEPA8260B-1996	Chromatography of gases-GC-MS	6890/5975

Note: USEPA is American National Environmental Protection Agency method.

Soil pollutant content after table 2 is repaired

Embodiment 3-14:

Contaminated site, prosthetic device, restorative procedure are substantially withembodiment 2, and concrete operations condition is different.

Concrete operations condition and experimental result are in Table 3.

Under table 3 different operating condition, the variation (mg/Kg) of front and back sample point benzene concentration is processed in experiment

Embodiment 15-26:

Contaminated site, prosthetic device, restorative procedure are substantially withembodiment 2, and difference is:

A plurality of heating extractors and injection-tube are pressed regular hexagon arranged distribution in repairing place; Concrete operations condition is different.

Concrete operations condition and experimental result are in Table 4.

Under table 4 different operating condition, the variation (mg/Kg) of front and back sample point chloroform concentration is processed in experiment

Claims (9)

Translated fromChinese

1.一种适用于高粘性污染土壤的射频加热气相抽提高级氧化原位修复装置，其特征在于：它包括一个或多个注射管，以及排布在注射管周围的多个加热抽提器；每个加热抽提器包括抽提管以及设在抽提管内的加热管，射频电极置于加热管中，射频电极通过同轴电缆与匹配器连接，匹配器通过同轴电缆与射频发射器连接；抽提管外壳上有多个开孔；抽提管内加热管外部装有填料和催化剂；抽提管内壁设有一层网眼大小比填料和催化剂粒径小的网格；所有抽提管上部的抽提连接管连接在一起，并与冷凝单元、气液分离器、真空泵顺序相连。1. A radio frequency heating gas phase extraction advanced oxidation in-situ remediation device suitable for highly viscous contaminated soil, characterized in that it includes one or more injection pipes, and a plurality of heating extractors arranged around the injection pipes ; Each heating extractor includes an extraction tube and a heating tube located in the extraction tube, the radio frequency electrode is placed in the heating tube, the radio frequency electrode is connected to the matcher through a coaxial cable, and the matcher is connected to the radio frequency transmitter through a coaxial cable Connection; there are multiple openings on the shell of the extraction tube; fillers and catalysts are installed outside the heating tube in the extraction tube; a layer of mesh with a mesh size smaller than the particle size of the filler and catalyst is provided on the inner wall of the extraction tube; The extraction connecting pipes are connected together, and connected with the condensing unit, gas-liquid separator, and vacuum pump in sequence.2.如权利要求1所述的适用于高粘性污染土壤的射频加热气相抽提高级氧化原位修复装置，其特征在于：注射管与加热抽提器之间按圆形或正六边形排列分布。2. The RF-heated gas-phase extraction advanced oxidation in-situ remediation device suitable for highly viscous polluted soil according to claim 1, characterized in that: the injection pipe and the heating extractor are arranged in a circular or regular hexagonal arrangement .3.如权利要求1或2所述的适用于高粘性污染土壤的射频加热气相抽提高级氧化原位修复装置，其特征在于：注射管管壁上设有开孔。3. The radio-frequency heating gas phase extraction advanced oxidation in-situ repair device suitable for highly viscous polluted soil according to claim 1 or 2, characterized in that: the wall of the injection pipe is provided with openings.4.如权利要求1或2所述的适用于高粘性污染土壤的射频加热气相抽提高级氧化原位修复装置，其特征在于：多个加热抽提器之间的间距为2～5米。4. The RF-heated gas-phase extraction advanced oxidation in-situ remediation device suitable for highly viscous polluted soil according to claim 1 or 2, characterized in that the distance between multiple heating extractors is 2-5 meters.5.一种使用如权利要求1-4所述的修复装置的适用于高粘性污染土壤的射频加热气相抽提高级氧化原位修复方法，其特征在于，它包括如下步骤：5. A radio-frequency heating gas phase pumping advanced oxidation in-situ repair method suitable for highly viscous contaminated soil using the repair device as claimed in claims 1-4, characterized in that it comprises the following steps:（一）根据污染土壤场地具体情况，将多个加热抽提器和注射管排列分布在修复场地中，多个加热抽提器之间的间距为2～5米；(1) According to the specific conditions of the contaminated soil site, arrange and distribute multiple heating extractors and injection pipes in the restoration site, and the distance between multiple heating extractors is 2 to 5 meters;（二）将所有加热抽提器的抽提连接管连接在一起，合并成一根共用连接管，再将该共用连接管与冷凝单元、气液分离器和真空泵顺序相连；(2) Connect the extraction connecting pipes of all heating extractors together to form a common connecting pipe, and then connect the common connecting pipe with the condensing unit, gas-liquid separator and vacuum pump in sequence;（三）将经研磨后的碳酸钙粉末通过注射管直接注射至高粘性污染土壤中，添加比例为土壤质量的10%～15%；(3) Inject the ground calcium carbonate powder directly into the highly viscous contaminated soil through the injection tube, and the addition ratio is 10% to 15% of the soil mass;（四）将质量浓度为30%的过硫酸钠溶液通过注射管直接注射至高粘性污染土壤中，添加比例为土壤质量的20%～25%；(4) Directly inject sodium persulfate solution with a mass concentration of 30% into the highly viscous contaminated soil through the injection tube, and the addition ratio is 20% to 25% of the soil mass;（五）先预热一段时间，再在加热的同时开启真空泵进行抽提，采用间歇抽提方式，控制加热源的温度为100～500℃，加热时间100～140小时；在负压状态下，将抽提出来的热蒸汽，经过冷凝单元、气液分离器，最后进入尾气处理设备中进行处理。(5) Preheat for a period of time, and then turn on the vacuum pump for extraction while heating, adopt the intermittent extraction method, control the temperature of the heating source to 100-500°C, and the heating time is 100-140 hours; under negative pressure, The extracted hot steam passes through the condensation unit, the gas-liquid separator, and finally enters the tail gas treatment equipment for treatment.6.如权利要求5所述的适用于高粘性污染土壤的射频加热气相抽提高级氧化原位修复方法，其特征在于，多个加热抽提器和注射管之间按圆形或正六边形排布。6. The radio-frequency heating gas phase extraction advanced oxidation in-situ repair method suitable for highly viscous polluted soil as claimed in claim 5, characterized in that, a plurality of heating extractors and injection pipes are arranged in a circular or regular hexagonal shape arranged.7.如权利要求6所述的适用于高粘性污染土壤的射频加热气相抽提高级氧化原位修复方法，其特征在于，间歇抽提方式为：每抽提12小时后，间隔12小时再抽。7. The radio frequency heating gas phase extraction advanced oxidation in-situ repair method suitable for highly viscous polluted soil as claimed in claim 6, characterized in that the intermittent extraction method is: after every 12 hours of extraction, the extraction is repeated at intervals of 12 hours .8.如权利要求7所述的适用于高粘性污染土壤的射频加热气相抽提高级氧化原位修复方法，其特征在于，控制加热源的温度为200℃；加热时间120小时。8. The radio frequency heating gas phase extraction advanced oxidation in-situ remediation method suitable for highly viscous polluted soil as claimed in claim 7, characterized in that the temperature of the heating source is controlled to be 200°C and the heating time is 120 hours.9.如权利要求8所述的适用于高粘性污染土壤的射频加热气相抽提高级氧化原位修复方法，其特征在于，对从气液分离器出来的冷凝液进行有机相的回收。9. The radio frequency heating gas phase extraction advanced oxidation in-situ remediation method suitable for highly viscous polluted soil as claimed in claim 8, characterized in that the organic phase is recovered from the condensate from the gas-liquid separator.

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