CN112479557A - Thickened oil sludge treatment method - Google Patents
Thickened oil sludge treatment method Download PDFInfo
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- CN112479557A CN112479557A CN202011549397.1A CN202011549397A CN112479557A CN 112479557 A CN112479557 A CN 112479557A CN 202011549397 A CN202011549397 A CN 202011549397A CN 112479557 A CN112479557 A CN 112479557A
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- oil
- oil sludge
- thick oil
- demulsifier
- water
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/14—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents
- C02F11/143—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents using inorganic substances
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/02—Biological treatment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/14—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents
- C02F11/147—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents using organic substances
Abstract
The invention discloses a method for treating thick oil sludge, which belongs to the field of harmless and recycling treatment of thick oil sludge and comprises the following steps: chemical separation, air flotation oil removal and plant restoration, which comprises the following steps: heating mixed liquid obtained after diluting thick oil sludge with water, adding sulfuric acid to adjust pH, adding a self-made demulsifier and a commodity coagulant, carrying out chemical separation under stirring, standing for layering after separation is completed, allowing floating oil on the uppermost layer to enter an oil storage tank, separating water and silt on the lower layer by using a centrifugal machine, allowing a centrifugate to further enter air flotation for oil removal, and allowing a mud cake to enter plant restoration. The oil content of mud cakes after phytoremediation is lower than 0.5 percent. The method adopts a chemical method, a physical method and a biological method to treat the thick oil sludge, and realizes the reclamation and the harmlessness of the thick oil sludge.
Description
Technical Field
The invention relates to the technical field of harmless and recycling treatment of thick oil sludge, in particular to a thick oil sludge treatment method.
Background
The thick oil sludge is typical oily sludge and is mainly generated in the processes of thick oil exploitation, transportation, storage, thick oil wastewater treatment and the like; contains wax, asphaltene, colloid, chemical agents such as scale inhibitor, coagulant, bactericide, etc., and is a stable system of oil-in-water and water-in-oil type. Oily sludge, which is randomly piled or improperly disposed without being treated, seriously harms the environment and human health, is brought into a hazardous waste management system. Harmful substances in the oily sludge, particularly high-concentration petroleum hydrocarbon, can poison soil microorganisms, reduce the types and the quantity of the soil microorganisms, further reduce the activity of soil invertase and reduce the ecological diversity of the soil. Polycyclic aromatic hydrocarbons in the oily sludge have genetic toxicity to organisms, and if entering the organisms, the polycyclic aromatic hydrocarbons cause ecotoxicity effects. Heavy metals in the oily sludge have strong toxicity and ecological accumulation effect, so that the oily sludge is more harmful. Petroleum hydrocarbons in the oily sludge can migrate in soil and can seep into underground water, and further pollute other water systems along with the flow of the underground water, so that the dissolved oxygen in the water body is reduced, the ecological environment of the water body is influenced, and aquatic organisms are threatened. When the pollutants in the oily sludge enter rivers or lakes in large quantity and exceed the maximum environmental capacity, the survival of aquatic organisms is seriously influenced, so that the aquatic organisms die and the diversity is reduced.
The oil content of the thick oil sludge is generally higher than 20 percent and can reach 50 percent at most, and the recovery value is high; but the components are complex, the viscosity is high, the particles are fine, the emulsification degree is high, and the dehydration is difficult. Most of petroleum substances can be recovered by solvent extraction, and the treatment cost is high due to the fact that an extracting agent is expensive and has certain loss in the treatment process; burning usually needs to consume combustion improver, the cost is high, and the risk of secondary pollution of smoke exists. The thermal desorption can effectively recover oil gas, but has high requirements on equipment and higher investment and operation cost; the solid-liquid separation method can recover most of petroleum in the oil sludge, the process is easy to realize, and the main research direction is to develop the demulsifier with high efficiency and low cost.
In recent years, along with the increase of the environmental protection of oil fields, the treatment method of the thick oil sludge has better development, but has various advantages and certain limitations, and the harmless treatment, the recycling and the reduction of the thick oil sludge are difficult to realize by only one process for single treatment.
Disclosure of Invention
The invention aims to provide a method for treating thick oil sludge, which aims to solve the problems in the prior art and realize the recycling and harmless treatment of the thick oil sludge.
In order to achieve the purpose, the invention provides the following scheme:
the invention provides a treatment method of thick oil sludge, which comprises three steps of chemical separation, air flotation oil removal and phytoremediation, and specifically comprises the following steps:
(1) chemical separation: diluting the thick oil sludge with 3-5 times of water by mass, stirring in a heating state, adjusting pH, adding a demulsifier and a flocculant, stirring, standing for layering, allowing upper-layer floating oil to enter an oil storage tank, and separating lower-layer water from silt to obtain a centrifugate and a mud cake;
(2) air flotation oil removal: carrying out air floatation oil removal on the centrifugate obtained in the step (1), after oil removal is finished, enabling upper-layer floating oil to enter an oil storage tank, and circulating lower-layer liquid for diluting water in chemical separation;
(3) plant restoration: and (2) performing phytoremediation on the mud cakes subjected to the chemical separation in the step (1), sowing landscape plant seeds, and performing conventional management and remediation.
Preferably, the demulsifier in step (1) is a self-made demulsifier, which is white powder at normal temperature and is easily soluble in water and acid, and Al2O320-25% by mass, and the pH of 10-15% aqueous solution is 3-5.
Preferably, the addition amount of the demulsifier is 0.3-0.5% of the mass of the thickened oil sludge.
Preferably, the flocculant comprises polyacrylamide or polyferric sulfate.
Preferably, the addition amount of the flocculant is 0.5-0.7% of the mass of the thick oil sludge.
Preferably, the heating temperature in step (1) is 70-80 deg.C, and the pH is adjusted to 5-6.
Preferably, the demulsifier and the flocculant are added in the step (1) and then stirred for 20-30 minutes.
Preferably, the air flow in the air floatation oil removal is 2.5-3m3·m-3·h-1The air floatation time is 20-30 minutes.
Preferably, the landscape plants comprise clover, miscanthus floridulus, miscanthus maculatus and narcissus.
The invention discloses the following technical effects:
compared with the prior art, the invention adopts the combination of chemical, physical and biological methods to treat the thick oil sludge, the oil-containing sludge is an emulsification system of water-in-oil and oil-in-water, and the demulsifier in the invention can effectively destroy the oil-water emulsification system and realize oil-water sludge layering. Firstly, diluting the thickened oil sludge with 3-5 times of water by mass, stirring the diluted thickened oil sludge at the heating state of 70-80 ℃, improving molecular motion in a system by heating, increasing the collision frequency of particles, being beneficial to destabilizing an emulsion system, reducing the viscosity of the oil sludge by heating, being beneficial to uniformly mixing a subsequent demulsifier and exerting the maximum effect; the air flotation oil removal is mainly physical treatment, common air is aerated into oil sludge emulsion, oil particles with the diameter of 0.25-25 mu m in the oil sludge emulsion fall off from silt, mainly dispersed oil and emulsified oil reach the surface of the emulsion along with bubbles, and the main function of the step is to further reduce petroleum substances in mud cakes and prepare for subsequent biological treatment; the final biological treatment is to utilize the absorption and degradation of plants, and the microorganisms in the soil and the root systems of the plants have symbiotic action in the process of plant restoration, and the microorganisms and the root systems are mutually dependent. On one hand, the petroleum substance has very high toxicity to plants, the toxic action received by the plants is greatly reduced due to the degradation and metabolism of the microorganisms of the root system to the petroleum substance, the plant secretion provides substrates and nutrient substances to the microorganisms, and the toxicity of the petroleum substance to the microorganisms is reduced. The process has the advantages of low treatment cost, strong operability, no waste liquid discharge in the treatment process, environmental protection and sanitation, and the treated mud cake can be used for planting clover and other landscape plants, thereby effectively realizing the reclamation and harmlessness of the thick oil sludge.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
The self-made demulsifier is white powder at normal temperature, and is easily soluble in water, acid and Al2O320-25% by mass, and the pH of 10-15% aqueous solution is 3-5.
Example 1
(1) The heavy oil sludge is obtained from oil extraction companies in certain oil fields in northeast China, and the water content, the oil content and the sediment content of the heavy oil sludge are respectively 8.23 percent, 41.32 percent and 50.45 percent. Weighing 50g of thick oil sludge in a 250ml beaker, adding 200ml of water for dilution, adding sulfuric acid for adjusting the pH to 5, and adding a self-made demulsifier (Al) with the oil sludge mass fraction of 0.7%2O320% by mass), 0.5% by mass of polyacrylamide. Stirring and heating up to 80 ℃, and slowly stirring and separating for 25 minutes. And standing for layering after separation is finished, wherein the floating oil on the uppermost layer enters an oil storage tank, the water and the silt on the lower layer are separated by a centrifugal machine, the centrifugate further enters air floatation for oil removal, the mud cake enters phytoremediation, and the oil content of the mud cake is 1.7%.
(2) Air flotation oil removal: after the centrifugate after chemical separation is processed by a heat exchange system to normal temperature, air flotation oil removal is carried out, and the air flow is 3m3·m-3·h-1The air floating time is 25 minutes, after oil removal, the upper layer floating oil enters an oil storage tank, and the lower layer liquid is circularly used for diluting water in chemical separation.
(3) Plant restoration: and (3) performing phytoremediation on the mud cakes after chemical separation, uniformly mixing the mud cakes with conventional soil in a ratio of 1:1, sowing clover seeds, performing conventional management and remediation for 120 days, and controlling the oil content of the soil to be 0.36% after completion.
Example 2
(1) The heavy oil sludge is obtained from oil extraction companies in certain oil fields in northeast China, and the water content, the oil content and the sediment content of the heavy oil sludge are respectively 8.67 percent, 39.65 percent and 51.68 percent. Weighing 50g of thick oil sludge in a 250ml beaker, adding 200ml of water for dilution, adding sulfuric acid for adjusting the pH to 6, and adding a self-made demulsifier (Al) with the oil sludge mass fraction of 0.6 percent2O325% by mass), 0.7% by mass of polyacrylamide. Stirring and heating to 75 deg.c for 30 min. Standing for layering after separation, allowing the uppermost layer of floating oil to enter an oil storage tank, allowing the lower layer of water and silt to undergo centrifugal separation, and allowing the centrifugate to further enterRemoving oil by air floatation, and repairing the mud cakes by plants, wherein the oil content of the mud cakes is 1.8 percent.
(2) Air flotation oil removal: after the centrifugate after chemical separation is processed by a heat exchange system to normal temperature, air flotation oil removal is carried out, and the air flow is 2.5m3·m-3·h-1The air floating time is 30 minutes, after oil removal, the upper layer floating oil enters an oil storage tank, and the lower layer liquid is circularly used for diluting water in chemical separation.
(3) Plant restoration: and (3) performing phytoremediation on the mud cakes after chemical separation, uniformly mixing the mud cakes with conventional soil in a ratio of 1:1, sowing clover seeds, performing conventional management and remediation for 120 days, and controlling the oil content of the soil to be 0.40% after completion.
Example 3
(1) The heavy oil sludge is obtained from oil extraction companies in certain oil fields in northeast China, and the water content, the oil content and the sediment content of the heavy oil sludge are respectively 8.35 percent, 42.21 percent and 49.44 percent. Weighing 50g of thick oil sludge in a 250ml beaker, adding 200ml of water for dilution, adding sulfuric acid for adjusting the pH to 5, and adding a self-made demulsifier (Al) with the oil sludge mass fraction of 0.7%2O322% by mass), 0.5% by mass of polyacrylamide. Stirring and heating up to 80 ℃, and slowly stirring and separating for 25 minutes. And standing for layering after separation is finished, wherein the floating oil on the uppermost layer enters an oil storage tank, the water and the silt on the lower layer are separated by a centrifugal machine, the centrifugate further enters air floatation for oil removal, the mud cake enters phytoremediation, and the oil content of the mud cake is 1.7%.
(2) Air flotation oil removal: after the centrifugate after chemical separation is processed by a heat exchange system to normal temperature, air flotation oil removal is carried out, and the air flow is 3m3·m-3·h-1The air floating time is 20 minutes, after oil removal, the upper layer floating oil enters an oil storage tank, and the lower layer liquid is circularly used for diluting water in chemical separation.
(3) Plant restoration: and (3) performing phytoremediation on the mud cakes after chemical separation, uniformly mixing the mud cakes with conventional soil in a ratio of 1:1, sowing miscanthus sinensis seeds, performing conventional management and remediation for 120 days, and obtaining the soil oil content of 0.38% after completion.
Comparative example 4
(1) The heavy oil sludge is obtained from oil extraction companies in certain oil fields in northeast China, and the water content, the oil content and the sediment content of the heavy oil sludge are divided into8.47%, 41.75% and 49.78%, respectively. Weighing 50g of thick oil sludge in a 250ml beaker, adding 200ml of water for dilution, adding sulfuric acid for adjusting the pH to 6, and adding a self-made demulsifier (Al) with the oil sludge mass fraction of 0.7 percent2O325% by mass), 0.6% by mass of polyacrylamide. Stirring and heating up to 80 ℃, and slowly stirring and separating for 25 minutes. And standing for layering after separation is finished, wherein the floating oil on the uppermost layer enters an oil storage tank, the water and the silt on the lower layer are separated by a centrifugal machine, the centrifugate further enters air floatation for oil removal, the mud cake enters phytoremediation, and the oil content of the mud cake is 1.7%.
(2) Air flotation oil removal: after the centrifugate after chemical separation is processed by a heat exchange system to normal temperature, air flotation oil removal is carried out, and the air flow is 2.5m3·m-3·h-1The air floating time is 25 minutes, after oil removal, the upper layer floating oil enters an oil storage tank, and the lower layer liquid is circularly used for diluting water in chemical separation.
(3) Plant restoration: and (3) performing phytoremediation on the mud cakes after chemical separation, uniformly mixing the mud cakes with conventional soil in a ratio of 1:1, sowing miscanthus floridulus seeds, performing conventional management and remediation for 120 days, and controlling the oil content of the soil to be 0.42% after completion.
Example 5
(1) The heavy oil sludge is obtained from oil extraction companies in certain oil fields in northeast China, and the water content, the oil content and the sediment content of the heavy oil sludge are respectively 8.09 percent, 45.25 percent and 46.66 percent. Weighing 50g of thick oil sludge in a 250ml beaker, adding 200ml of water for dilution, adding sulfuric acid for adjusting the pH to 5, and adding a self-made demulsifier (Al) with the oil sludge mass fraction of 0.6 percent2O322% by mass), 0.6% by mass of polyacrylamide. Stirring and heating up to 80 ℃, and slowly stirring and separating for 25 minutes. And standing for layering after separation is finished, wherein the floating oil on the uppermost layer enters an oil storage tank, the water and the silt on the lower layer are separated by a centrifugal machine, the centrifugate further enters air floatation for oil removal, the mud cake enters phytoremediation, and the oil content of the mud cake is 1.7%.
(2) Air flotation oil removal: after the centrifugate after chemical separation is processed by a heat exchange system to normal temperature, air flotation oil removal is carried out, and the air flow is 3m3·m-3·h-1Air floatation time is 25 min, after oil removal, the upper layer floating oil enters an oil storage tank, and the lower layer liquid is circulated for chemical separationThe diluting water in (1).
(3) Plant restoration: and (3) performing phytoremediation on the mud cakes after chemical separation, uniformly mixing the mud cakes with conventional soil in a ratio of 1:1, sowing narcissus seeds, performing conventional management and remediation for 120 days, and controlling the oil content of the soil to be 0.41 percent after completion.
After the heavy oil sludge is repaired in the embodiment, the oil content of the soil is measured after conventional management (conventional watering, fertilization and the like) is finished, the oil content of the soil is lower than 0.5%, and the method can be used for agriculture.
Comparative example
The chemical separation step is the same as that in example 1, except that the self-made demulsifier in step (1) is replaced by sodium dodecyl benzene sulfonate, and the oil content of the mud cake after the chemical separation is finished is 11.9%.
Comparative example 2
The chemical separation step is the same as that in example 2, except that the self-made demulsifier in step (1) is replaced by ferrous chloride, and the oil content of the mud cake after the chemical separation is finished is 10.5%.
Comparative example 3
The chemical separation step is the same as that in example 3, except that the self-made demulsifier in the step (1) is replaced by polyvinyl alcohol, and the oil content of the mud cake after the chemical separation is finished is 12.3%.
Comparative example 4
The chemical separation step is the same as the example 4, except that the self-made demulsifier in the step (1) is replaced by span-80, and the oil content of the mud cake after the chemical separation is finished is 11.8%.
Comparative example 5
The chemical separation step is the same as example 5, except that the homemade demulsifier in step (1) is replaced by OP-10, and the oil content of the mud cake after the chemical separation is finished is 12.9%.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (9)
1. The treatment method of the thick oil sludge is characterized by comprising three steps of chemical separation, air flotation oil removal and phytoremediation, and comprises the following steps:
(1) chemical separation: diluting the thick oil sludge with 3-5 times of water by mass, stirring in a heating state, adjusting pH, adding a demulsifier and a flocculant, stirring, standing for layering, allowing upper-layer floating oil to enter an oil storage tank, and separating lower-layer water from silt to obtain a centrifugate and a mud cake;
(2) air flotation oil removal: performing air flotation oil removal on the centrifugate obtained in the step (1), after oil removal, enabling upper-layer floating oil to enter an oil storage tank, and circulating lower-layer liquid for later use;
(3) plant restoration: and (2) performing phytoremediation on the mud cakes subjected to the chemical separation in the step (1), sowing landscape plant seeds, and performing conventional management and remediation.
2. The method for treating thick oil sludge according to claim 1, wherein the demulsifier in step (1) is a self-made demulsifier which is in a white powder state at normal temperature and is easily soluble in water and acid, and Al2O320-25% by mass, and the pH of 10-15% aqueous solution is 3-5.
3. The method for treating thick oil sludge according to claim 2, wherein the addition amount of the demulsifier is 0.5-0.7% of the mass of the thick oil sludge.
4. The method for treating thick oil sludge according to claim 1, wherein the flocculant comprises polyacrylamide or polyferric sulfate.
5. The method for treating thick oil sludge according to claim 4, wherein the addition amount of the flocculant is 0.5-0.7% of the mass of the thick oil sludge.
6. The method for treating thick oil sludge according to claim 1, wherein the heating temperature in step (1) is 70-80 ℃, and the pH is adjusted to 5-6.
7. The method for treating thick oil sludge according to claim 1, wherein the demulsifier and the flocculant are added in the step (1) and then stirred for 20-30 minutes.
8. The method for treating thick oil sludge according to claim 1, wherein the gas flow rate in the air flotation oil removal is 2.5-3m3·m-3·h-1The air floatation time is 20-30 minutes.
9. The method for treating thick oil sludge according to claim 1, wherein the landscape plants comprise clover, miscanthus floridulus, miscanthus maculatus and narcissus.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114426384A (en) * | 2022-02-08 | 2022-05-03 | 河南省高新技术实业有限公司 | Method for treating oil sludge |
| WO2024047742A1 (en) * | 2022-08-30 | 2024-03-07 | 清水建設株式会社 | Method for treating oil-containing sludge, method for recovering oil from oil-containing sludge, apparatus for treating oil-containing sludge, apparatus for recovering oil from oil- containing sludge, system for treating oil-containing sludge, and system for recovering oil from oil-containing sludge |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102627381A (en) * | 2012-04-26 | 2012-08-08 | 陕西科技大学 | Two-step method resource treatment process for sludge containing oil |
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- 2020-12-24 CN CN202011549397.1A patent/CN112479557A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102627381A (en) * | 2012-04-26 | 2012-08-08 | 陕西科技大学 | Two-step method resource treatment process for sludge containing oil |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114426384A (en) * | 2022-02-08 | 2022-05-03 | 河南省高新技术实业有限公司 | Method for treating oil sludge |
| WO2024047742A1 (en) * | 2022-08-30 | 2024-03-07 | 清水建設株式会社 | Method for treating oil-containing sludge, method for recovering oil from oil-containing sludge, apparatus for treating oil-containing sludge, apparatus for recovering oil from oil- containing sludge, system for treating oil-containing sludge, and system for recovering oil from oil-containing sludge |
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Application publication date: 20210312 |