CN113070333A - Cooperative thermal desorption combined vacuum remediation method for petroleum hydrocarbon contaminated soil - Google Patents

Cooperative thermal desorption combined vacuum remediation method for petroleum hydrocarbon contaminated soil Download PDF

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CN113070333A
CN113070333A CN202110293277.8A CN202110293277A CN113070333A CN 113070333 A CN113070333 A CN 113070333A CN 202110293277 A CN202110293277 A CN 202110293277A CN 113070333 A CN113070333 A CN 113070333A
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soil
thermal desorption
petroleum hydrocarbon
treatment
vacuum
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张亚平
陈春红
沈凯
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Southeast University
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09C—RECLAMATION OF CONTAMINATED SOIL
    • B09C1/00—Reclamation of contaminated soil
    • B09C1/005—Extraction of vapours or gases using vacuum or venting

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  • Life Sciences & Earth Sciences (AREA)
  • Soil Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

The invention relates to a synergic thermal desorption combined vacuum remediation method for petroleum hydrocarbon contaminated soil, which comprises the following steps: the method comprises the following steps: adjusting the water content of the petroleum hydrocarbon polluted soil, and crushing, grinding and screening to obtain a standby soil sample; step two: adding Ca (OH) to the soil sample for use2Carrying out modification treatment to obtain modified soil; ca (OH)2The adding amount is 0.1 wt% -1 wt% of the weight of the spare soil sample; step three: and carrying out thermal desorption treatment on the modified soil at 350-500 ℃, wherein the vacuum degree of a thermal desorption atmosphere is 30-80kPa, and cooling after the thermal desorption treatment to obtain the restored soil. The invention is realized by Ca (OH)2The modifier is used for modifying the petroleum hydrocarbon polluted soil, and then thermal treatment restoration is carried out by a thermal desorption combined vacuum strengthening method, so that the restoration effect is strengthened, the desorption efficiency is improved, and the method has the characteristics of high restoration efficiency, good restoration effect and the like.

Description

Cooperative thermal desorption combined vacuum remediation method for petroleum hydrocarbon contaminated soil
Technical Field
The invention relates to the technical field of reinforced thermal desorption combined remediation, in particular to a method for synergistic thermal desorption combined vacuum remediation of petroleum hydrocarbon contaminated soil.
Background
During exploration, production, transportation and storage, petroleum hydrocarbons are released into the environment. In addition, the soil and underground water pollution caused by the artificial carelessness and the intentional discharge of industrial wastewater also cause the pollution of petroleum hydrocarbon soil and underground water, and the soil pollution caused by the petroleum hydrocarbon seriously influences the survival and the life health of human beings, thereby being a great environmental problem to be solved urgently. Thus, a variety of soil remediation methods have evolved including chemical oxidation, phytoremediation, electroremediation, bioremediation, soil leaching, surfactant extraction, and thermal desorption. However, some methods cannot completely treat a complicated petroleum hydrocarbon-contaminated site due to slow treatment speed, large environmental side effects, low efficiency, and the like.
Compared to other thermal treatments such as incineration (600-. In the prior art, the heterotopic thermal desorption process mainly aims at the thermal desorption of polychlorinated biphenyls (PCBs) and Polycyclic Aromatic Hydrocarbons (PAHs), and adopts means such as nitrate assistance and microbial remediation, and the like, so that the problems of high culture difficulty of a strain culture medium, complex operation steps, weak operability, long period, high energy consumption and low efficiency exist. In addition, research on the Total Petroleum Hydrocarbon (TPHs) contaminated soil enhanced thermal desorption process and the influencing factors thereof is relatively few, so research on the Total Petroleum Hydrocarbon (TPHs) contaminated soil enhanced thermal desorption method is necessary.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a synergic thermal desorption combined vacuum remediation method for petroleum hydrocarbon contaminated soil, and solves the technical problems of high energy consumption and low remediation efficiency of the existing remediation method.
The technical scheme adopted by the invention is as follows:
a cooperative thermal desorption combined vacuum remediation method for petroleum hydrocarbon contaminated soil comprises the following steps:
the method comprises the following steps: pretreating the polluted soil, adjusting the water content of the petroleum hydrocarbon polluted soil, and crushing, grinding and screening to obtain a spare soil sample;
step two: adding Ca (OH) to the soil sample for use2Carrying out modification treatment to obtain modified soil; ca (OH)2The adding amount is 0.1 wt% -1 wt% of the weight of the spare soil sample;
step three: and carrying out thermal desorption treatment on the modified soil at 350-500 ℃, wherein the vacuum degree of a thermal desorption atmosphere is 30-80kPa, and cooling after the thermal desorption treatment to obtain the restored soil.
In the first step, the soil moisture content of the petroleum hydrocarbon polluted soil is adjusted to 10% -20%.
And (3) sieving the stones with a 20-mesh sieve in the step one, wherein the particle size of the sieved soil is less than 0.9 mm.
In the second step, Ca (OH) is added into the spare soil sample2Then, the mixture was stirred by an inverting shaker at a stirring speed of 30 rpm.
In the third step, the thermal desorption treatment time is 10-60 min; and after thermal desorption treatment, cooling to room temperature to obtain the restored soil.
In the third step, the vacuum degree of the thermal desorption atmosphere is 60-80 kPa.
The invention has the following beneficial effects:
according to the invention, a certain amount of modifier is used in modification treatment, and the removal efficiency of pollutants can be improved by combining vacuum enhanced thermal desorption, so that the remediation target is achieved, and compared with the method only adopting an ex-situ thermal desorption technology, the method can reduce a large amount of energy consumption and reduce the soil remediation cost. Meanwhile, the invention has the advantages of high repair efficiency, good repair effect, low energy consumption and the like. Ca (OH) during ex situ thermal desorption remediation of petroleum hydrocarbon contaminants in soil2Middle Ca2+The soil cement is a good soil cement, can loosen soil, promote structural change of the soil, improve hardening condition of the soil in a thermal desorption process, and increase a mass transfer process. Simultaneously, at high temperature and Ca (OH)2Under the synergistic effect of the components, the petroleum hydrocarbon is more beneficial to desorption of the petroleum hydrocarbon due to the base catalytic decomposition effect in the thermal desorption process. By Ca (OH)2The soil after the modification pretreatment is treated by a thermal desorption and vacuum reinforcement combined method, so that the polluted soil remediation efficiency is higher, the petroleum hydrocarbon remediation efficiency can reach 99.8 percent, the efficiency is improved, and the remediation period is shorter.
Drawings
FIG. 1 shows the process of the present invention Ca (OH)2Graph of the effect of addition on the efficiency of petroleum hydrocarbon removal as a function of temperature.
FIG. 2 is a graph of the effect of vacuum on the efficiency of petroleum hydrocarbon removal as a function of temperature for the process of the present invention.
FIG. 3 is a graph of the effect of petroleum hydrocarbon removal efficiency on temperature using different methods.
Fig. 4 is a flow chart of the present invention.
Detailed Description
The following describes specific embodiments of the present invention.
As shown in fig. 4, the cooperative thermal desorption combined vacuum remediation method for petroleum hydrocarbon contaminated soil of the invention comprises the following steps:
the method comprises the following steps: pretreating the polluted soil, adjusting the water content of the petroleum hydrocarbon polluted soil, and crushing, grinding and screening to obtain a spare soil sample;
step two: adding Ca (OH) into the spare soil sample2Carrying out modification treatment to obtain modified soil; ca (OH)2The adding amount is 0.1 wt% -1 wt% of the weight of the spare soil sample;
step three: treating the modified soil by adopting a thermal desorption combined vacuum strengthening method, performing thermal desorption treatment on the modified soil at 350-500 ℃, wherein the vacuum degree of the thermal desorption atmosphere is 30-80kPa, and cooling after the thermal desorption treatment to obtain the restored soil.
As a specific implementation manner, the thermal desorption combined vacuum strengthening process flow comprises the following steps: carrying out thermal desorption treatment on the polluted soil by adopting a tubular furnace, and opening a nitrogen carrier gas and a vacuum pump before heating so as to maintain a certain vacuum degree in the tubular furnace; then weighing a certain amount of soil sample in a tube furnace for thermal desorption treatment, and adjusting the air pressure in the furnace by continuous vacuumizing operation in the heating (thermal desorption) process so as to maintain the corresponding vacuum degree.
Example 1
(1) Air-drying the petroleum hydrocarbon polluted soil, adjusting to obtain soil with the water content of 10-20%, crushing, grinding, and sieving with a 20-mesh sieve to obtain a spare soil sample with the particle size of less than 0.9 mm;
(2) adding Ca (OH) into the spare soil sample2Performing soil sample modification treatment, Ca (OH)2The adding amount is 0.1 wt% of the weight of the standby soil sample, and the soil sample enters an overturning oscillator to be stirred after being addedStirring at the rotating speed of 30rpm to obtain modified soil;
(3) and carrying out thermal desorption treatment on the modified soil at 350 ℃, wherein the vacuum degree of a thermal desorption atmosphere is 30kPa, and cooling to room temperature after 20min of thermal desorption treatment to obtain the restored soil.
Example 2
(1) Air-drying the petroleum hydrocarbon polluted soil, adjusting to obtain soil with the water content of 10-20%, crushing, grinding, and sieving with a 20-mesh sieve to obtain a spare soil sample with the particle size of less than 0.9 mm;
(2) adding Ca (OH) into the spare soil2Performing soil sample modification treatment, Ca (OH)2The adding amount is 0.5 wt% of the weight of the spare soil sample, and the mixture is stirred in a turnover oscillator at the stirring speed of 30rpm to obtain modified soil;
(3) and carrying out thermal desorption treatment on the modified soil at 400 ℃, wherein the vacuum degree of the thermal desorption atmosphere is 60kPa, and cooling to room temperature after heat treatment for 40min to obtain the restored soil.
Example 3
(1) Air-drying the petroleum hydrocarbon contaminated soil, adjusting to obtain soil with the water content of 10-20%, crushing, grinding, and sieving with a 20-mesh sieve to obtain standby contaminated soil with the particle size of less than 0.9 mm;
(2) adding Ca (OH) into the spare soil2Performing soil sample modification treatment, Ca (OH)2Adding the soil sample into the soil sample in an amount of 1 wt% of the weight of the soil sample, and then stirring the soil sample in a turnover oscillator at a stirring speed of 30rpm to obtain modified soil;
(3) and carrying out thermal desorption treatment on the modified soil at 450 ℃, wherein the vacuum degree of the thermal desorption atmosphere is 80kPa, and cooling to room temperature after heat treatment for 40min to obtain the restored soil.
Example 4
(1) Air-drying the petroleum hydrocarbon contaminated soil, adjusting to obtain soil with the water content of 10-20%, crushing, grinding, and sieving with a 20-mesh sieve to obtain standby contaminated soil with the particle size of less than 0.9 mm;
(2) adding Ca (OH) into the spare soil2Performing soil sample modification treatment, Ca (OH)2The addition amount of the soil sample is standby1 wt% of the modified soil is added and then stirred in a turnover oscillator at the stirring speed of 30rpm to obtain the modified soil;
(3) and carrying out thermal desorption treatment on the modified soil at 500 ℃, wherein the vacuum degree of the thermal desorption atmosphere is 80kPa, carrying out heat treatment for 50min, and cooling to room temperature to obtain the restored soil.
Comparative example 1
(1) Air-drying the petroleum hydrocarbon contaminated soil, adjusting to obtain soil with the water content of 10-20%, crushing, grinding, and sieving with a 20-mesh sieve to obtain standby contaminated soil with the particle size of less than 0.9 mm;
(2) and (3) performing thermal desorption treatment on the standby polluted soil at 450 ℃, and cooling to room temperature after 40min to obtain the restored soil.
Ca (OH) in example 32Compared with the ex-situ thermal desorption method in the comparative example 1, the method has the advantages that the removal efficiency of the petroleum hydrocarbon can be improved from 71.4% to 91.3% under the same desorption temperature and time conditions, and the desorption efficiency of the soil polluted by the petroleum hydrocarbon is remarkably improved, namely Ca (OH)2Under the condition of ensuring the repair quality by cooperating with thermal desorption and vacuum reinforcement, the aims of saving energy, reducing consumption and reducing repair cost can be achieved by reducing the thermal desorption temperature or reducing the thermal desorption time.
Comparative example 2
(1) Air-drying the petroleum hydrocarbon contaminated soil, adjusting to obtain soil with the water content of 10-20%, crushing, grinding, and sieving with a 20-mesh sieve to obtain standby contaminated soil with the particle size of less than 0.9 mm;
(2) and (3) performing thermal desorption treatment on the standby polluted soil at 500 ℃, and cooling to room temperature after 50min to obtain the restored soil.
Ca (OH) in example 32Compared with the ectopic thermal desorption technology in the comparative example 2, the synergistic ectopic thermal desorption combined vacuum strengthening method has the advantages that the removal efficiency of petroleum hydrocarbon is 91.3 percent and 89.7 percent respectively, the removal efficiency is not very different, and Ca (OH) is proved2Indeed, the synergistic heterotopic thermal desorption combined with vacuum reinforcement can achieve desorption efficiency equivalent to higher thermal desorption temperature and longer thermal desorption time through the synergistic effect of the modifier and the vacuum reinforcement.
Comparative example 3
(1) Air-drying the petroleum hydrocarbon contaminated soil, adjusting to obtain soil with the water content of 10-20%, crushing, grinding, and sieving with a 20-mesh sieve to obtain standby contaminated soil with the particle size of less than 0.9 mm;
(2) and (3) carrying out thermal desorption treatment on the standby polluted soil at 500 ℃, carrying out thermal desorption treatment under the vacuum degree of 80kPa, carrying out heat treatment for 50min, and cooling to room temperature to obtain the restored soil.
The comparative example 3 adopts vacuum strengthening synergistic thermal desorption to repair the soil polluted by the petroleum hydrocarbon, the removal efficiency of the petroleum hydrocarbon is 96.2 percent, which is higher than the removal rate of the petroleum hydrocarbon in the comparative example 1 without any strengthening effect, which is 71.4 percent, and thus, the removal efficiency of the petroleum hydrocarbon can be obviously enhanced by the vacuum combined thermal desorption technology. Meanwhile, example 4 shows Ca (OH)2The effect of the modifier in cooperation with thermal desorption and vacuum reinforcement on improving the petroleum hydrocarbon removal efficiency is superior to that of thermal desorption and vacuum reinforcement. Fig. 2 shows that the thermal desorption efficiency increases with increasing vacuum. When the temperature is lower than 300 ℃, the enhancement effect of the vacuum degree on the petroleum hydrocarbon removal efficiency is not obvious, when the temperature is higher than 400 ℃, the enhancement effect of different vacuum degrees is obviously different, and the enhancement effect of the high vacuum degree (60kPa and 80kPa) is obviously higher than that of the low vacuum degree (30kPa and 50 kPa).
Comparative example 4
(1) Air-drying the petroleum hydrocarbon contaminated soil, adjusting to obtain soil with the water content of 10-20%, crushing, grinding, and sieving with a 20-mesh sieve to obtain standby contaminated soil with the particle size of less than 0.9 mm;
(2) adding Ca (OH) into the spare soil2Performing soil sample modification treatment, Ca (OH)2The adding amount is 1 wt%, and the mixture enters an overturning oscillator for stirring after being added, wherein the stirring speed is 30rpm, so that the modified soil is obtained;
(3) and (3) carrying out thermal desorption treatment on the modified contaminated soil at 500 ℃, and cooling to room temperature after 50min to obtain the restored soil.
Comparative example 4 use of Ca (OH)2The removal efficiency of the petroleum hydrocarbon polluted soil treated by the synergistic heterotopic thermal desorption technology is 91.9 percent, which is compared with the implementationExample 4 uses medium Ca (OH)2The removal rate of petroleum hydrocarbon by combining the synergistic ectopic thermal desorption and the vacuum reinforcement is 7.9 percent, which proves that Ca (OH)2The effect of restoring the petroleum hydrocarbon polluted soil by combining thermal desorption with vacuum reinforcement is the best. FIG. 1 shows the thermal desorption removal efficiency of petroleum hydrocarbon according to Ca (OH)2The addition amount is increased, wherein 1% of Ca (OH)2The strengthening effect of the modified contaminated soil is optimal, and the strengthening effect is better when the temperature is higher.
FIG. 3 is a graph of the efficiency of petroleum hydrocarbon removal as a function of temperature for different processes. As can be seen from FIG. 3, Ca (OH)2Synergistic thermal desorption, vacuum enhanced thermal desorption and Ca (OH)2The three repairing methods of synergy thermal desorption and vacuum all have strengthening effect on the removal efficiency of petroleum hydrocarbon. When the thermal desorption temperature is 500 ℃ and the desorption time is 30min, the removal rates corresponding to the three repair methods are respectively 90.5%, 94.4% and 97.7%, and compared with the removal rate of 78.6% of unmodified and unreinforced ectopic thermal desorption under the same conditions, the removal rates are respectively improved by 11.9%, 15.8% and 19.1%, which shows that Ca (OH)2The synergistic thermal desorption and vacuum reinforcement has the best reinforcing effect on the removal rate of petroleum hydrocarbon, so that the repair quality can be ensured, the repair temperature and time can be reduced, the energy consumption and repair cost of original ex-situ thermal desorption are reduced, the damage of thermal desorption on the soil function, structure and ecosystem is weakened, and the soil can be recycled.
Test results
Examples 1-4 repair cases were as follows:
Figure BDA0002981797120000041
comparative examples 1-4 repair cases were as follows:
Figure BDA0002981797120000042
Figure BDA0002981797120000051

Claims (6)

1. a cooperative thermal desorption combined vacuum remediation method for petroleum hydrocarbon contaminated soil is characterized by comprising the following steps:
the method comprises the following steps: adjusting the water content of the petroleum hydrocarbon polluted soil, and crushing, grinding and screening to obtain a standby soil sample;
step two: adding Ca (OH) to the soil sample for use2Carrying out modification treatment to obtain modified soil; ca (OH)2The adding amount is 0.1 wt% -1 wt% of the weight of the spare soil sample;
step three: and carrying out thermal desorption treatment on the modified soil at 350-500 ℃, wherein the vacuum degree of a thermal desorption atmosphere is 30-80kPa, and cooling after the thermal desorption treatment to obtain the restored soil.
2. The cooperative thermal desorption combined vacuum remediation method of petroleum hydrocarbon contaminated soil as claimed in claim 1, wherein in the first step, the soil moisture content of the petroleum hydrocarbon contaminated soil is adjusted to 10% -20%.
3. The method for cooperative thermal desorption combined vacuum remediation of petroleum hydrocarbon contaminated soil as claimed in claim 1, wherein the stone is sieved through a 20-mesh sieve in the first step, and the particle size of the sieved soil is less than 0.9 mm.
4. The method for cooperative thermal desorption combined vacuum remediation of petroleum hydrocarbon contaminated soil as claimed in claim 1, wherein in step two, Ca (OH) is added to the spare soil sample2Then, the mixture was stirred by an inverting shaker at a stirring speed of 30 rpm.
5. The cooperative thermal desorption combined vacuum remediation method for petroleum hydrocarbon contaminated soil as claimed in claim 1, wherein in the third step, the thermal desorption treatment time is 10-60 min; and after thermal desorption treatment, cooling to room temperature to obtain the restored soil.
6. The method for cooperative thermal desorption combined vacuum remediation of petroleum hydrocarbon contaminated soil as claimed in claim 1, wherein in step three, the thermal desorption atmosphere vacuum degree is 60-80 kPa.
CN202110293277.8A 2021-03-18 2021-03-18 Cooperative thermal desorption combined vacuum remediation method for petroleum hydrocarbon contaminated soil Pending CN113070333A (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016186242A1 (en) * 2015-05-18 2016-11-24 한국철도기술연구원 Thermal desorption system for polluted soil and ballast, using microwave indirect-irradiation method, and thermal desorption method for polluted soil and ballast, using system
CN106807738A (en) * 2016-12-23 2017-06-09 镇江华域环保设备制造有限公司 A kind of in-situ remediation method of organic material contaminated soil
CN108817058A (en) * 2018-07-05 2018-11-16 上海艾库环境工程有限公司 A kind of soil remediation method
CN109513736A (en) * 2018-12-05 2019-03-26 上海万帝环境技术有限公司 Contaminated soil remediation method and prosthetic device
CN111872093A (en) * 2020-06-16 2020-11-03 江苏省环境科学研究院 Method for restoring petroleum hydrocarbon polluted soil
CN111957726A (en) * 2020-07-22 2020-11-20 杨德敏 In-situ combined remediation method for petroleum-polluted soil

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016186242A1 (en) * 2015-05-18 2016-11-24 한국철도기술연구원 Thermal desorption system for polluted soil and ballast, using microwave indirect-irradiation method, and thermal desorption method for polluted soil and ballast, using system
CN106807738A (en) * 2016-12-23 2017-06-09 镇江华域环保设备制造有限公司 A kind of in-situ remediation method of organic material contaminated soil
CN108817058A (en) * 2018-07-05 2018-11-16 上海艾库环境工程有限公司 A kind of soil remediation method
CN109513736A (en) * 2018-12-05 2019-03-26 上海万帝环境技术有限公司 Contaminated soil remediation method and prosthetic device
CN111872093A (en) * 2020-06-16 2020-11-03 江苏省环境科学研究院 Method for restoring petroleum hydrocarbon polluted soil
CN111957726A (en) * 2020-07-22 2020-11-20 杨德敏 In-situ combined remediation method for petroleum-polluted soil

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Application publication date: 20210706