CN114573213B - Treating agent and treating method for oily sludge treatment - Google Patents
Treating agent and treating method for oily sludge treatment Download PDFInfo
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- CN114573213B CN114573213B CN202210489176.2A CN202210489176A CN114573213B CN 114573213 B CN114573213 B CN 114573213B CN 202210489176 A CN202210489176 A CN 202210489176A CN 114573213 B CN114573213 B CN 114573213B
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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
- C02F11/148—Combined use of inorganic and organic substances, being added in the same treatment step
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Abstract
The invention discloses a treating agent for treating oily sludge, which comprises the following components: sodium bicarbonate: 45-60 parts by weight; fatty alcohol polyoxyethylene ether: 10-15 parts by weight; dimethyl dioctadecyl ammonium bromide: 8-10 parts by weight; sodium polysulfide: 5-8 parts by weight. The treating agent can reduce the residual oil content of the oil sludge which is difficult to treat and has the oil content of more than 15wt% to below 1.5wt%, and is particularly suitable for the treatment and resource utilization of aged oil sludge in oil fields and oil refineries. The invention also discloses a method for treating the oily sludge by using the treating agent.
Description
Technical Field
The invention belongs to the field of oil sludge treatment, and particularly relates to an oil sludge treatment agent and a treatment method.
Background
The petroleum and petrochemical industry often produces oily sludge, often referred to simply as oil sludge, such as aged oil sludge from oil extraction and storage, tank bottom oil sludge, and heavily contaminated soil from crude oil in oil fields, etc., and the aged oil sludge and tank bottom oil sludge are essentially also deposited as underground soil components mixed into crude oil. The oil content of these sludges is usually at least 15wt%, and may even be as high as 40wt%, with gross statistics on the million ton level of sludge produced per year in china alone. If the oil sludge is discarded at will, the oil sludge not only pollutes the environment, but also is a great waste to the oil contained in the oil sludge. Therefore, it is desired to recover the petroleum in the sludge and regenerate the soil so that the soil can be recovered as pollution-free soil for agricultural production.
The petrochemical oily sludge is typically treated by a chemical heat treatment process (commonly referred to in the art as a chemical heat washing process). The chemical agent heat treatment method is mainly characterized in that hot water with the temperature of 45-60 ℃ is used for soaking oil sludge, meanwhile, a special treatment agent (generally called chemical heat washing agent in the industry) is added, the purpose of oil-water-sludge three-phase separation is achieved by utilizing the action mechanisms of wetting inversion, emulsification washing and the like of the treatment agent and assisting the thermal and mechanical actions, so that the petroleum in the oil sludge is recovered, and meanwhile, the soil is regenerated. The chemical hot washing reagent is usually prepared by compounding strong base (the pH value of a 1% aqueous solution is more than 12) and a surfactant with strong emulsifying capacity. The action mechanism is mainly emulsification cleaning, crude oil attached to argillaceous particles is emulsified into a water phase, the cleaning mechanism causes that a large amount of cleaning sewage (generally more than 2 times of the amount of the oil sludge) which is difficult to treat is formed after chemical hot cleaning of the oil sludge, the cleaning sewage is stable in emulsification, high in emulsified oil content, and a certain amount of fine argillaceous particles are mixed. The chemical hot washing treatment oil sludge has poor effect, which is mainly reflected in that the adaptability to the oil sludge with higher oil content is not strong, the washing effect on the oil sludge with oil content of more than 15 percent is poor, and the national standard requirement of the oil sludge oil content of less than 2 percent by weight after washing is difficult to achieve. And more chemical hot washing reagent is forcibly added, so that the effect is not great, the oil content of the treated oil sludge is not reduced when the oil content is reduced to about 1.4wt%, and the phenomenon of diminishing marginal effect exists between the addition amount of the chemical hot washing reagent and the oil content of the treated oil sludge.
The present invention has been made to solve the above problems.
Disclosure of Invention
The invention provides a treating agent for oily sludge treatment, which comprises the following components:
sodium bicarbonate: 45-60 parts by weight;
fatty alcohol polyoxyethylene ether: 10-15 parts by weight;
dimethyl dioctadecyl ammonium bromide: 8-10 parts by weight;
sodium polysulfide: 5-8 parts by weight.
Preferably: the sodium polysulfide being Na2S4Or Na2S5。
Preferably, the treating agent for oily sludge treatment further comprises 4-8 parts by weight of sodium humate.
Wherein the treating agent for oily sludge treatment does not contain a strongly basic substance such as NaOH.
Among them, sodium bicarbonate plays a role in creating a weak alkaline environment (pH lower than 11) and assisting in emulsification of crude oil.
The fatty alcohol-polyoxyethylene ether is a common surfactant, and can gradually strip crude oil coated on the surface of soil particles by using the amphiphilic action of the fatty alcohol-polyoxyethylene ether, so that the crude oil gradually enters a water phase to play a role in extracting and recovering the crude oil. Fatty alcohol polyoxyethylene ethers are commercially available, for example, under the trade designation AEO-9.
The dimethyl dioctadecyl ammonium bromide plays a role in dispersion and displacement, and the dispersion refers to maintaining the suspension dispersion state of the oil sludge in hot water in the chemical hot washing process, avoiding sedimentation and enabling the oil sludge to be in full contact with hot water and a treating agent dissolved in the hot water; displacement means that it also helps to strip the crude oil from the soil particle surface.
More preferably, the treating agent for oily sludge treatment is characterized by further comprising the following substances: calcium bicarbonate: 12-16 parts by weight; ammonium hexametaphosphate: 1.4-2.6 parts by weight: terpineol: 0.5-1.4 parts by weight, but these three substances are not essential components, but are optimized for certain specific oily sludges, wherein the calcium bicarbonate pH buffer acts and assists in settling loose gritty particles mixed in the oily sludge, wherein the sodium hexametaphosphate helps to maintain a dispersed suspension of certain particularly fine sludge particles, wherein the terpineol helps to form an oil-water emulsion, facilitating separation of the oil-water emulsion phase from the solid phase.
In a second aspect, the present invention provides a treatment method for oily sludge treatment, comprising the steps of:
1) feeding oily sludge into a stirring tank containing hot water with the temperature of 40-60 ℃, wherein the mass of the hot water is 8-20 times that of the oily sludge, adding the treating agent for treating the oily sludge according to the first aspect of the invention into the hot water, controlling the adding amount of the treating agent to be 2-3 wt% of the weight of the crude oil sludge, and stirring for 20-30 minutes;
2) and (3) sending the treated mixture into a solid-liquid separator for solid-liquid separation, wherein the obtained liquid phase is an oil-water mixed phase, and the obtained solid phase is the treated oily sludge.
Preferably, if the oil content of the treated oil-containing sludge is further reduced, a step 3) can be further included after the step 2):
3) adding hot water of hot water at the temperature of 40-60 ℃ and the treating agent for oily sludge treatment according to the first aspect of the invention into the treated oily sludge, wherein the weight of the hot water is 1-3 times of the weight of the treated oily sludge, the weight of the treating agent is 0.4-0.6 wt% of the weight of the treated oily sludge, and stirring for 3-8 minutes and then carrying out solid-liquid separation to obtain sludge with the oil content of less than 0.3 wt%.
Preferably, the oil-water mixed phase is subjected to demulsification and phase separation and then oil-water separation, so that crude oil recovery is realized.
A particular feature of the present invention is the addition of sodium polysulfide, based on intensive studies conducted by the inventors on the source of the above-mentioned diminishing marginal effect of conventional treating agents. The inventor researches and discovers that the existing form of crude oil in the oil sludge can be subdivided into two forms, the predominant one is thick crude oil wrapped outside soil particles, the crude oil is easy to wash away due to easy contact with a treating agent, and the removal amount of the crude oil is in positive correlation with the amount of the treating agent. The other is crude oil existing in the pores inside the soil particles, which is less than usual but difficult to wash away by the treating agent, and is a source of residual oil content. The inventor researches and discovers that the oil sludge is mainly a mixture of crude oil and soil, wherein soil substances are dispersed in the oil sludge, but the soil substances are still in a particle aggregate structure that a plurality of basic soil particles are glued together by soil colloidal particles, the soil colloidal particles are various naturally-occurring colloidal substances in the soil, such as layered aluminosilicate as a main chemical component of the colloidal particles, gel silicate and oxide and humus combined with iron, aluminum and the like, the colloidal particles are just used for aggregating tiny rock fragments to form particle aggregates, and the particle aggregates are used for forming the soil. Crude oil has high viscosity and is difficult to enter the pores inside the particle aggregates, but because many oily sludge is accumulated over years or even decades, the crude oil is slowly infiltrated into the pores inside the particle aggregates and is difficult to enter the pores, the crude oil occupies the pores inside the particle aggregates in a long contact process, the contact area between a surfactant in a treating agent and the surfactant in the treating agent is limited in a short time of chemical heat washing, the dissolving and displacing effects on the surfactant are limited, and the crude oil content in the cleaned oil sludge is difficult to further reduce by adding a large amount of the treating agent.
The inventors have surprisingly found that the addition of sodium polysulphide can solve the above problems. After addition of sodium polysulfide, it was found that the residual oil content in the treated oil sludge could be reduced to 1.4wt% or less. It is presumed that this may be due to the fact that sodium polysulfide loses its viscosity after interacting with the colloidal particles of soil, resulting in disintegration of the aggregates of particles, and the crude oil originally retained in the pores of the aggregates of soil particles is sufficiently exposed to the treating agent to interact with the surfactant in the treating agent into the liquid phase.
The addition of sodium black humate to the treatment agent can be used in conjunction with sodium polysulfide to further break down the aggregates of particles, which presumably interact with humic acid species in the soil colloid to reduce their viscosity and promote disintegration. The sodium humate can be compounded with sodium polysulfide, and the residual oil content in the treated oil sludge can be reduced to below 1.0 wt%.
The invention has the following beneficial effects:
1. the introduction of sodium polysulfide component into the treating agent can reduce the oil content of the treated oil sludge to below 1.4 wt%.
2. Sodium humate is further introduced into the treating agent and can be matched with sodium polysulfide to reduce the oil content of the treated oil sludge to below 1.0 wt%.
3. Sodium polysulfide and sodium black humate are environment-friendly substances, and are remained in the treated oil sludge and can be just used as a soil sulfur supplement agent and a fertilizer, sulfur is an essential micronutrient element in soil, many chemical fertilizers also need to be specially added with a sulfur element to supplement sulfur, and sodium polysulfide can be oxidized into elemental sulfur, sulfite or sulfate ions under the environmental condition and can be just used as a sulfur supplement agent, so that the treated oil sludge can be recovered into soil for agricultural use.
4. In some preferred schemes, the added ammonium hexametaphosphate remains in the treated oil sludge and can also be used as a phosphate fertilizer and a nitrogenous fertilizer, so that the treated oil sludge can be recovered into soil for agricultural use.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the following embodiments are provided for a detailed description to facilitate the understanding of the skilled person.
Example 1
The aged oil sludge near the well mouth of certain Liaoning Tujin oil field is brown and black, the average oil content is 17wt%, and the aged oil sludge is treated by chemical hot washing at 50 deg.C. The hot water amount is 10 times of the mass of the oil sludge, the treating agent of the invention is added into the hot water, the using amount of the treating agent is 2 percent of the mass of the oil sludge, and the treating agent comprises the following components: sodium bicarbonate: 45 parts by weight; fatty alcohol polyoxyethylene ether AEO-9: 10 parts by weight; dimethyl dioctadecyl ammonium bromide: 8 parts by weight; sodium polysulfide (Na)2S4：Na2S5=1: 2): 5 parts by weight. The chemical hot washing is carried out in an intermittent stirring tank, mechanical stirring is carried out, the rotating speed of a stirring paddle is 10rpm, the chemical hot washing time is 20 minutes, all the treated oil-water-sludge mixture enters a subsequent solid-liquid separator for separation, a solid phase (namely the treated oil sludge) is separated from a liquid phase (an oil-water mixed phase), and the oil-water mixed phase is subjected to emulsion breaking and phase splitting and then oil-water separation. The residual oil content of the solid phase is measured to be 1.3wt%, which meets the national standard of less than 2 wt%.
Comparative example 1
The sludge to be treated and the chemical hot washing conditions were the same as in example 1 except that no sodium polysulfide was added to the treating agent and the contents of the other treating agent components were the same as in example 1. After treatment, the residual oil content of the solid phase measured by the method is 2.8wt%, which does not meet the national standard of less than 2 wt%.
Example 2
The aged oil sludge cleaned during the tank bottom desilting of a crude oil storage tank in a certain Liaoning Panjin oil refinery is sticky with a dark color, the oil content is measured to be 23wt% on average, and the chemical hot washing process is carried out at 60 ℃ considering that the oil content is too high and the chemical hot washing force needs to be increased. The hot water amount is 10 times of the mass of the oil sludge, the treating agent of the invention is added into the hot water, the using amount of the treating agent is 2 percent of the mass of the oil sludge, and the treating agent comprises the following components: sodium bicarbonate: 60 parts by weight; fatty alcohol polyoxyethylene ether AEO-9: 15 parts by weight; dimethyl dioctadecyl ammonium bromide: 10 parts by weight; sodium polysulfide (Na)2S4：Na2S5=1: 2): 8 parts by weight. The chemical hot washing is carried out in an intermittent stirring tank, mechanical stirring is carried out, the rotating speed of a stirring paddle is 10rpm, the chemical hot washing time is 20 minutes, all the treated oil-water-sludge mixture enters a subsequent solid-liquid separator for separation, a solid phase (namely the treated oil sludge) is separated from a liquid phase (an oil-water mixed phase), and the oil-water mixed phase is subjected to emulsion breaking and phase splitting and then oil-water separation. The residual oil content of the oil is 1.4wt% by taking a solid phase for measurement, and the oil meets the national standard of less than 2 wt%.
Comparative example 2
The sludge to be treated and the chemical hot washing conditions were the same as in example 2 except that sodium polysulfide was not added to the treating agent and the content of the remaining treating agent components was the same as in example 2. After treatment, the residual oil content of the solid phase measured by the method is 3.4wt%, which does not meet the national standard of less than 2 wt%.
Example 3
The aged oil sludge near the well mouth of certain Liaoning Tujin oil field is brown and black, the average oil content is 17wt%, and the aged oil sludge is treated by chemical hot washing at 50 deg.C. The hot water amount is 10 times of the mass of the oil sludge, the treating agent is added into the hot water, the using amount of the treating agent is 2 percent of the mass of the oil sludge, and the treating agent comprises the following components: sodium bicarbonate: 45 parts by weight; fatty alcohol polyoxyethylene ether AEO-9: 10 parts by weight; dimethyl dioctadecyl ammonium bromide: 8 parts by weight; sodium polysulfide（Na2S4：Na2S5=1: 2): 5 parts by weight of sodium humate and 4 parts by weight of sodium humate. The chemical hot washing is carried out in an intermittent stirring tank, mechanical stirring is carried out, the rotating speed of a stirring paddle is 10rpm, the chemical hot washing time is 20 minutes, all the treated oil-water-sludge mixture enters a subsequent solid-liquid separator for separation, a solid phase (namely the treated oil sludge) is separated from a liquid phase (an oil-water mixed phase), and the oil-water mixed phase is subjected to demulsification and phase separation and then oil-water separation. The residual oil content of the oil is measured by taking a solid phase to be 0.94wt%, which meets the national standard of less than 2 wt%.
Example 4
Aged oil sludge near a wellhead of an oilfield in certain desert of Clama, Xinjiang is a brown and black sticky matter, the oil content is measured to be 14wt% on average, and the aged oil sludge is treated by a chemical hot washing process at 50 ℃. The hot water amount is 10 times of the mass of the oil sludge, and the following two treating agents are added into the hot water, and the dosage of the treating agents is 2 percent of the mass of the oil sludge: the reagent A is a treating agent of the invention and comprises the following components: sodium bicarbonate: 45 parts by weight; fatty alcohol polyoxyethylene ether AEO-9: 10 parts by weight; dimethyl dioctadecyl ammonium bromide: 8 parts by weight; sodium polysulfide (Na)2S4：Na2S5=1: 2): 5 parts by weight; and the reagent B is sodium bicarbonate: 45 parts by weight; fatty alcohol polyoxyethylene ether AEO-9: 10 parts by weight; dimethyl dioctadecyl ammonium bromide: 8 parts by weight, in comparison with reagent A, only in the absence of addition of sodium polysulfide. The chemical hot washing is carried out in an intermittent stirring tank, mechanical stirring is carried out, the rotating speed of a stirring paddle is 10rpm, the chemical hot washing time is 20 minutes, all the treated oil-water-sludge mixture enters a subsequent solid-liquid separator for separation, a solid phase (namely the treated oil sludge) is separated from a liquid phase (an oil-water mixed phase), and the oil-water mixed phase is subjected to emulsion breaking and phase splitting and then oil-water separation. And measuring the residual oil content of the oil sludge by using a solid phase, and finding that the oil content of the oil sludge treated by the reagent A is 1.3wt% and the oil content of the oil sludge treated by the reagent B is 1.4wt%, and both the oil content and the oil content meet the national standard of less than 2 wt%. The reason for this analysis may be the lack of humus and silica-alumina gel-like sticky particles in the desert soil, which is itself based on highly loose sand grains, without particle aggregates, and is self-supportingHowever, crude oil in the gaps of the particle aggregates does not exist, so that all crude oil is only wrapped outside the sand particles and is easily washed away by the treating agent, and the oil contents of the A, B oil sludge after the two hot washing agents are treated are not greatly different. This also indicates from one side that polysulfides may act to promote chemical hot washing by disrupting the tackiness of the colloidal particles in the soil.
Example 5
The aged oil sludge near the well mouth of certain oil field in eastern Shandong province is brown and black viscous matter, the measured average oil content is 17wt%, and the aged oil sludge is treated at 50 deg.c through chemical hot washing process. The hot water amount is 10 times of the mass of the oil sludge, the treating agent of the invention is added into the hot water, the using amount of the treating agent is 2 percent of the mass of the oil sludge, and the treating agent comprises the following components: sodium bicarbonate: 45 parts by weight; fatty alcohol polyoxyethylene ether AEO-9: 10 parts by weight; dimethyl dioctadecyl ammonium bromide: 8 parts by weight; sodium polysulfide (Na)2S4：Na2S5=1: 2): 5 parts by weight, 12 parts by weight of calcium bicarbonate, 1.4 parts by weight of ammonium hexametaphosphate and 0.5 part by weight of terpineol. The chemical hot washing is carried out in an intermittent stirring tank, mechanical stirring is carried out, the rotating speed of a stirring paddle is 10rpm, the chemical hot washing time is 20 minutes, all the treated oil-water-sludge mixture enters a subsequent solid-liquid separator for separation, a solid phase (namely the treated oil sludge) is separated from a liquid phase (an oil-water mixed phase), and the oil-water mixed phase is subjected to emulsion breaking and phase splitting and then oil-water separation. The residual oil content of the solid phase is measured to be 1.2wt%, which meets the national standard of less than 2 wt%.
Finally, it is noted that the above-mentioned preferred embodiments illustrate rather than limit the invention, and that, although the invention has been described in detail with reference to the above-mentioned preferred embodiments, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the scope of the invention as defined by the appended claims.
Claims (7)
1. The treating agent for treating the oily sludge is characterized by comprising the following components in parts by weight:
sodium bicarbonate: 45-60 parts by weight;
fatty alcohol polyoxyethylene ether: 10-15 parts by weight;
dimethyl dioctadecyl ammonium bromide: 8-10 parts by weight;
sodium polysulfide: 5-8 parts by weight, wherein the sodium polysulfide is Na2S4Or Na2S5。
2. The agent for oily sludge treatment according to claim 1, characterized in that it does not contain NaOH.
3. The agent for oily sludge treatment according to claim 1, characterized by further comprising 9 to 15 parts by weight of sodium humate.
4. The agent for oily sludge treatment according to claim 1, characterized by further comprising:
calcium bicarbonate: 12-16 parts by weight;
ammonium hexametaphosphate: 1.4-2.6 parts by weight:
terpineol: 0.5 to 1.4 weight portions.
5. A treatment method for oily sludge treatment is characterized by comprising the following steps:
1) feeding oily sludge into a stirring tank filled with hot water of 40-60 ℃, wherein the mass of the hot water is 8-20 times that of the oily sludge, adding the treating agent for treating the oily sludge according to claim 1 into the hot water, controlling the adding amount of the treating agent to be 2-3 wt% of the weight of the crude oil sludge, and stirring for 20-30 minutes;
2) and (3) sending the treated mixture into a solid-liquid separator for solid-liquid separation, wherein the obtained liquid phase is an oil-water mixed phase, and the obtained solid phase is the treated oily sludge.
6. The method for treating oily sludge according to claim 5, further comprising step 3) after step 2):
3) adding hot water of 40-60 ℃ and the treating agent for oily sludge treatment according to claim 1 into the treated oily sludge, wherein the weight of the hot water is 1-3 times of the weight of the treated oily sludge, the weight of the treating agent is 0.4-0.6 wt% of the weight of the treated oily sludge, and stirring for 3-8 minutes and then carrying out solid-liquid separation to obtain the sludge with the oil content of less than 0.3 wt%.
7. The method as claimed in claim 5, wherein the oil-water mixture is subjected to demulsification and phase separation, and then oil-water separation, thereby recovering crude oil.
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| CN103121780A (en) * | 2013-03-13 | 2013-05-29 | 天津市朗敦环保科技有限公司 | Oil sludge treatment method |
| RU2015143630A (en) * | 2013-03-14 | 2017-04-27 | Шеврон Ю.Эс.Эй. Инк. | PROCESS, METHOD AND SYSTEM FOR REMOVING HEAVY METALS FROM OIL CONTAINING SOLIDS |
| US10724314B1 (en) * | 2013-03-15 | 2020-07-28 | Rio Resources Llc | Method and apparatus for collection, treatment, and recycling of oilfield drilling fluids and wastewater |
| CN103979768B (en) * | 2014-05-27 | 2015-03-18 | 陕西延长石油（集团）有限责任公司 | Method for tempering oily sludge blended with coal water slurry |
| CN106277709A (en) * | 2016-07-20 | 2017-01-04 | 西安华诺环保股份有限公司 | A kind of disposal of oily sludge environment-friendly cleaning agent and preparation method thereof |
| CN106281332A (en) * | 2016-07-27 | 2017-01-04 | 武汉都市环保工程技术股份有限公司 | Mercury contaminated soil reparation passivator and mercury contaminated soil restorative procedure and application |
| CN110484264A (en) * | 2019-07-08 | 2019-11-22 | 南京迪天高新产业技术研究院有限公司 | A kind of passivator and preparation method thereof for repairing farming land Heavy Metals in Soil Contaminated chromium |
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