CN107162365B - Preparation method and use method of sludge oil removal agent - Google Patents
Preparation method and use method of sludge oil removal agent Download PDFInfo
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- CN107162365B CN107162365B CN201710538805.5A CN201710538805A CN107162365B CN 107162365 B CN107162365 B CN 107162365B CN 201710538805 A CN201710538805 A CN 201710538805A CN 107162365 B CN107162365 B CN 107162365B
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F11/00—Treatment of sludge; Devices therefor
Abstract
The invention discloses a preparation method of a sludge oil removing agent in the field of oil field oily sludge treatment, and the sludge oil removing agent comprises the following components in percentage by weight: 0.1-1 wt% of hydroxymethyl alkyl glycoside; the cross-linked fatty alcohol-polyoxyethylene block polyether accounts for 0.1-1 wt%; 0.1-5 wt% of sodium carbonate; potassium pyrophosphate in an amount of 0.01 to 0.1 wt%; the balance of water; the hydroxymethyl alkyl glycoside is prepared by modifying alkyl glycoside. The invention also discloses a using method of the sludge oil removing agent, which comprises the steps of mixing the oily sludge and the sludge oil removing agent, placing the mixture into a constant-temperature reaction tank, enabling the reaction temperature of the reaction tank to be 45-50 ℃, enabling the stirring speed to be 200-450 r/min, fully washing the oily sludge for 1-2 h, enabling the mixture in the reaction tank to stand for 1-3 h, enabling the mixture to be sequentially divided into three layers of oil, water and sludge from top to bottom, recycling the oil on the upper layer, discharging the sludge on the lower layer, and removing the oil in the oily sludge. The hydroxymethyl alkyl glycoside is compounded with other agents, so that the oil removing effect is enhanced, and the cost is lower.
Description
Technical Field
The invention belongs to the field of oil-containing sludge treatment in oil fields, and particularly relates to a preparation method and a use method of a sludge oil removing agent.
Background
The petrochemical industry of China produces a large amount of oily sludge every year, the yield is increased year by year, the oily sludge serving as a pollutant in the national hazardous waste list must be treated, otherwise, the oily sludge can affect the surrounding environment and production areas to different degrees, the oily sludge is also a waste of resources, oil components in the sludge are effectively separated and recovered, and the waste of resources can be reduced, and the precondition for carrying out harmless treatment and resource utilization of the oily sludge is also provided.
In recent years, researchers at home and abroad carry out a great deal of research work on sludge oil removal, and a plurality of treatment methods are formed. In the field of sludge oil removal, a quenching and tempering separation method, a biological treatment method, an incineration method, a solvent extraction oil recovery method and a coking method modification treatment technology are mainly adopted at home and abroad, but from the aspect of application effect, the following problems exist: the biological treatment method has the disadvantages of difficult selection of strains, overlong treatment period and difficult adaptation to sludge with high oil content; the incineration method has high treatment cost and operation cost, and secondary pollution such as SO2, CO, dust and the like can be generated in the treatment process; the solvent extraction recovery method has long flow, complex process, high solvent price and high treatment cost; the coking method has high treatment investment cost and complex process.
The medicament treatment is a low-cost oil recovery mode recognized at home and abroad, and the development of high-efficiency medicaments is a key problem and is also a practical problem of sludge oil removal on site at present. In the prior art, the medicament is adopted to treat the oily sludge, the required medicament application concentration is high, and the environmental temperature also needs to be controlled within a specified interval, so that the cost is overhigh. The invention patent of application No. 201210023784.0, application No. 2012.02.03 in Chinese patent database discloses a treatment method of oil-containing sludge in oil field, in the method, the oil-containing sludge needs to be filtered again after being primarily filtered, the oil-containing sludge passes through a screen twice at 90-120 ℃, a medicament is added, then the oil is removed by heating to 45-60 ℃, only 50% of crude oil in the oil-containing sludge can be recovered, the oil removal rate of the sludge is low, the steps are complex, and the cost is high. The invention patent of application No. 201010601322.3, application No. 2010.12.17 discloses an oily sludge thermochemical separating agent and a using method thereof, the oily sludge thermochemical separating agent prepared by the method can be used for treating oily sludge, particularly oil tank bottom sludge, can reduce the residual oil rate of bottom filling oil sludge to 0.5 percent at most, and still can not reach less than 0.3 percent of the requirement of GB4284 standard.
Disclosure of Invention
One of the purposes of the invention is to provide a preparation method of a sludge oil removal agent, which is characterized in that alkyl glycoside is modified to synthesize surfactant hydroxymethyl alkyl glycoside, the hydroxymethyl alkyl glycoside is compounded with other agents to enhance the oil removal effect, the oil-water interfacial tension of the sludge oil removal agent prepared by compounding is lower, the oil content of the treated sludge is lower than 0.3 percent, and the sludge oil removal agent meets the national standard; the sludge oil removing agent has lower concentration of each component, and reduces the cost required by on-site sludge oil removal.
The purpose of the invention is realized as follows: a preparation method of a sludge oil removing agent comprises the following steps: 0.1-1 wt% of hydroxymethyl alkyl glycoside; AEO-7 or peregal is 0.1-1 wt%; 0.1-5 wt% of sodium carbonate; potassium pyrophosphate in an amount of 0.01 to 0.1 wt%; the balance of water; the sum of the percentage contents of the components of the sludge oil removing agent is hundred; the hydroxymethyl alkyl glycoside is prepared by modifying alkyl glycoside.
According to the invention, alkyl glycoside is modified to prepare hydroxymethyl alkyl glycoside, the hydroxymethyl alkyl glycoside is a surfactant, and can play a role in addition and synergism with AEO-7 or peregal which is also a surfactant, so that the oil-water interfacial tension is further reduced, the capability of the surfactant penetrating into the surface and the interior of sludge is improved, the sludge dispersion effect is enhanced, the oil stripping effect on the surface and the interior of the sludge is improved, the surface adhesive force of oil on a muddy contact surface is reduced, the oil is separated from the muddy surface, the oil-containing sludge is separated into 3 layers of oil, water and sludge, the oil in the sludge is more thoroughly separated, the oil content of the treated sludge is lower than 0.3%, and the sludge conforms to the national standard GB 4284; the sludge oil removing agent has low concentration of each component, low cost for preparing the sludge oil removing agent and reduced cost required by on-site sludge oil removal.
As a further development of the invention, the alkyl glycoside is modified by:
1) weakly oxidized alkyl glycoside: dissolving an alkyl glycoside solution with the mass fraction of 45-50% in ethanol, stirring for 5-15 min, adding a Sarett reagent into the solution, wherein the volume ratio of the alkyl glycoside solution to the ethanol is 1: 1.5-1.8, and the feeding mass ratio of the alkyl glycoside to the Sarett reagent is (0.002-0.004): 1, and continuously stirring the solution for 1-3 h until the alkyl glycoside is weakly oxidized;
2) nucleophilic addition: adding 35-40% of formaldehyde aqueous solution into the weak oxidation product obtained in the step 1), wherein the volume ratio of the formaldehyde aqueous solution to the initial alkyl glycoside solution obtained in the step 1) is (1-1.33) to 1, slowly adding 4-6% of NaOH ethanol solution into the solution, wherein the volume ratio of the NaOH ethanol solution to the formaldehyde aqueous solution is 1 to (1.5-2), heating and refluxing, controlling the temperature of the mixed solution at 25-35 ℃, and fully stirring to ensure that carbanions of the weak oxidation product perform nucleophilic addition on formaldehyde;
3) reduction: adding sodium borohydride powder into the mixture obtained after the nucleophilic addition reaction in the step 2), adding 1.5-1.8 g of sodium borohydride into every 100ml of alkyl glycoside solution initially selected in the step 1), stirring the mixture for 3-5 hours under the cooling condition of ice-water bath, reducing aldehyde ketone into alcohol by using the sodium borohydride, purifying the product of the reduction reaction, and finally obtaining hydroxymethyl alkyl glycoside.
The alkyl glycoside is weakly oxidized by the Sarett reagent, the alkyl glycoside after the weak oxidation and formaldehyde are subjected to nucleophilic addition, and then the alkyl glycoside is reduced by sodium borohydride to complete the modification of the alkyl glycoside, so that the hydroxymethyl alkyl glycoside is prepared, the step for synthesizing the hydroxymethyl alkyl glycoside is simple, and the synthesis cost is low.
As an improvement of the present invention, the reaction occurring in the alkyl glycoside modification process is:
the surfactant hydroxymethyl alkyl glycoside is synthesized by a basic method of organic chemistry, the synthetic route is simple, the raw materials are easy to obtain, and the cost is lower.
As a further improvement of the present invention, the alkyl glycoside in step 1) is prepared by the following steps: mixing glucose and long-chain alkyl alcohol according to a molar ratio of 1 (1-20), stirring and heating to 45-135 ℃, adding an acid catalyst, continuously stirring, wherein the molar ratio of the glucose to the acid catalyst is 1 (0.1-0.5), carrying out acetal dehydration reaction on the glucose and the long-chain alkyl alcohol to generate an alkyl glycoside crude product, removing unreacted long-chain alkyl alcohol through a dealcoholization system, and carrying out decoloration treatment to obtain an alkyl glycoside finished product. The glucose and the long-chain alkyl alcohol are subjected to acetal dehydration reaction to prepare the alkyl glycoside, the glucose and the long-chain alkyl alcohol are easy to obtain and have low cost, substances polluting the environment are not generated during the reaction, and the biological environment is more friendly.
As a preferred embodiment of the present invention, the long-chain alkyl alcohol is hexanol, octanol, nonanol or decanol.
In a preferred embodiment of the present invention, the acidic catalyst is p-toluenesulfonic acid or benzenesulfonic acid.
As a further improvement of the invention, the hydroxymethyl alkyl glycoside is purified in step 3) by column chromatography or molecular distillation.
As a preferred embodiment of the invention, AEO-7 or peregal are both fatty alcohol polyoxyethylene block polyethers.
The invention also aims to provide a use method of the sludge oil removal agent prepared by the method, the sludge oil removal agent and the oily sludge are mixed in the reaction tank, the reaction temperature, the stirring speed and the reaction time of the reaction tank are controlled, the oil in the sludge is removed more thoroughly, and the oil content of the treated sludge is reduced to be below 0.3%.
The purpose of the invention is realized as follows: a use method of a sludge oil removing agent comprises the following steps:
mixing oil-containing sludge and a sludge oil removing agent according to a mass ratio of 1 (2-4), placing the mixture into a constant-temperature reaction tank, setting the reaction temperature of the reaction tank to be 45-50 ℃, and the stirring speed to be 200-450 r/min, fully washing the oil-containing sludge for 1-2 h, standing the mixture in the reaction tank for 1-3 h, sequentially dividing the mixture into three layers of oil, water and sludge from top to bottom, recovering the oil on the upper layer through a drainage groove on the upper part of the reaction tank, and discharging the sludge on the lower layer through a sludge discharge pipe on the lower part of the reaction tank to remove the oil in the oil-containing sludge.
According to the invention, the oily sludge is washed in the reaction tank by the sludge oil removing agent, the oily sludge is sequentially divided into three layers of oil, water and sludge from top to bottom after standing, the oil on the upper layer is recovered by the drainage groove on the upper part of the reaction tank, the oil can be recycled, resources are saved, and the sludge on the lower layer is discharged by the sludge discharge pipe on the lower part of the reaction tank; after the sludge oil removing agent is mixed with the oily sludge, water is mixed into the oily sludge, the oily sludge contains three phases of oil, water and sludge, hydroxymethyl alkyl glycoside is a surfactant and can be compounded with AEO-7 or peregal which is also a surfactant to play a role of addition and synergy, so that the oil-water interfacial tension is further reduced, the capability of the surfactant penetrating into the surface and the interior of the sludge is improved, the sludge dispersion effect is enhanced, the sludge surface and interior oil stripping effect is improved, the surface adhesive force of oil on a muddy contact surface is reduced, the oil is separated from the muddy surface, floating separation is carried out, the oily sludge is finally divided into 3 layers of oil, water and sludge, the oil in the sludge is more thoroughly separated, the oil content of the treated sludge is lower than 0.3 percent, and the national standard GB4284 is met; the sludge oil removing agent has low concentration of each component, low cost for preparing the sludge oil removing agent and reduced cost required by on-site sludge oil removal.
As a further improvement of the invention, the oily sludge and the sludge oil removing agent are mixed according to the following steps:
1) the mass of the oily sludge to be deoiled is m1, the mass of the sludge deoiling agent required to be prepared is m2 according to the mass ratio of the oily sludge to the sludge deoiling agent being 1 (2-4), and hydroxymethyl alkyl glycoside, AEO-7 or peregal, sodium carbonate, potassium pyrophosphate and water with the same application amount are prepared according to the components and the content of the sludge deoiling agent;
2) adding the water prepared in the step 1) into a reaction tank, sequentially adding half of the amount of sodium carbonate and all potassium pyrophosphate in the step 1), adding the oily sludge to be deoiled into the reaction tank, and stirring and mixing the solid-liquid mixture added into the reaction tank uniformly;
3) continuously adding the hydroxymethyl alkyl glycoside, AEO-7 or peregal prepared in the step 1) and the residual sodium carbonate into the reaction tank in sequence, and uniformly stirring and mixing the oily sludge and the sludge oil removal agent.
When the sludge oil removing agent and the oily sludge are mixed, firstly adding all potassium pyrophosphate and half of the amount of sodium carbonate into a reaction tank, then putting the oily sludge to be treated into the reaction tank, and finally sequentially adding hydroxymethyl alkyl glycoside, AEO-7 or peregal and the rest of sodium carbonate into the reaction tank; by adding sodium carbonate in two steps, the oily sludge can be more fully washed, the oil removal effect is improved by 10%, the oil content of the washed sludge is lower than 0.3%, and the national standard GB4284 is met.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of the hydroxymethyl alkyl glycoside synthesized by the present invention.
Detailed Description
Example 1
In the preparation method of the sludge oil removing agent of the embodiment, the composition and content of the sludge oil removing agent are as follows: hydroxymethyl alkyl glycoside 0.1 wt%; AEO-7 at 0.1 wt%; 1 wt% of sodium carbonate; potassium pyrophosphate 0.05 wt%; the balance of water; the sum of the percentage contents of the components of the sludge oil removing agent is hundred; the hydroxymethyl alkyl glycoside is prepared by modifying alkyl glycoside. The alkyl glycoside is modified by the following steps:
1) weakly oxidized alkyl glycoside: dissolving an alkyl glycoside solution with the mass fraction of 48.5% in ethanol, stirring for 10min, adding a Sarett reagent into the solution, wherein the feeding mass ratio of the alkyl glycoside to the Sarett reagent is 0.003: 1, and continuously stirring the solution for 2h until the alkyl glycoside is weakly oxidized; the alkyl glycoside is prepared by the following steps: mixing glucose and hexanol according to a molar ratio of 1:10, stirring and heating to 90 ℃, adding p-toluenesulfonic acid, continuously stirring, wherein the molar ratio of the glucose to the p-toluenesulfonic acid is 1: 0.3, carrying out acetal dehydration reaction on the glucose and the hexanol to generate an alkyl glycoside crude product, removing unreacted hexanol through a dealcoholization system, and decolorizing to obtain an alkyl glycoside finished product;
2) nucleophilic addition: adding a formaldehyde aqueous solution with the mass fraction of 37% into the weak oxidation product obtained in the step 1), wherein the volume ratio of the formaldehyde aqueous solution to the initial alkyl glycoside solution obtained in the step 1) is 1.16: 1, slowly adding a NaOH ethanol solution with the concentration of 5% into the solution, wherein the volume ratio of the NaOH ethanol solution to the formaldehyde aqueous solution is 1: 1.75, heating and refluxing, controlling the temperature of the mixed solution at 30 ℃, and fully stirring to ensure that carbanions of the weak oxidation product perform nucleophilic addition on formaldehyde;
3) reduction: adding sodium borohydride powder into the mixture after the nucleophilic addition reaction in the step 2), adding 1.66g of sodium borohydride into every 100ml of alkyl glycoside solution initially selected in the step 1) according to the adding amount of the sodium borohydride powder, stirring the mixture for 4 hours under the cooling condition of an ice-water bath, reducing aldehyde ketone into alcohol by the sodium borohydride, purifying the product of the column chromatography reduction reaction, and finally obtaining the hydroxymethyl alkyl glycoside.
The reaction in the modification process of the alkyl glycoside is as follows:
the method for treating the oily sludge by using the sludge oil removing agent comprises the following steps: selecting oil-containing sludge with 10.0wt% of oil content, 80wt% of water content and 10wt% of mud content in an oil field sludge drying pool, mixing the oil-containing sludge and a sludge oil removing agent according to the mass ratio of 1:2, placing the mixture in a constant-temperature reaction tank, and mixing the oil-containing sludge and the sludge oil removing agent according to the following steps:
1) the mass of the oily sludge to be deoiled is m1Calculating the mass m of the sludge oil-removing agent to be prepared according to the mass ratio of 1:2 of the oil-containing sludge to the sludge oil-removing agent2=2 m1According to the components and the content of the sludge oil removing agent, hydroxymethyl alkyl glycoside, AEO-7, sodium carbonate, potassium pyrophosphate and water are prepared in the same application amount;
2) adding the water prepared in the step 1) into a reaction tank, sequentially adding half of the amount of sodium carbonate and all potassium pyrophosphate in the step 1), adding the oily sludge to be deoiled into the reaction tank, and stirring and mixing the solid-liquid mixture added into the reaction tank uniformly;
3) continuously adding the hydroxymethyl alkyl glycoside prepared in the step 1), AEO-7 and the residual sodium carbonate into the reaction tank in sequence, and uniformly stirring and mixing the oily sludge and the sludge oil removal agent.
Setting the reaction temperature of a reaction tank at 50 ℃ and the stirring speed of 200 r/min, fully washing the oily sludge for 1.5h, standing the mixture in the reaction tank for 1h to ensure that the mixture is sequentially divided into three layers of oil, water and sludge from top to bottom, recovering the oil on the upper layer through a drainage groove on the upper part of the reaction tank, discharging the sludge on the lower layer through a sludge discharge pipe on the lower part of the reaction tank, and testing the oil content of the sludge on the lower layer after oil removal to be 0.21%.
Example 2
In the preparation method of the sludge oil removing agent of the embodiment, the composition and content of the sludge oil removing agent are as follows: hydroxymethyl alkyl glycoside 0.2 wt%; the peregal is 0.2 wt%; 2wt% of sodium carbonate; potassium pyrophosphate 0.01 wt%; the balance of water; the sum of the percentage contents of the components of the sludge oil removing agent is hundred; the hydroxymethyl alkyl glycoside is prepared by modifying alkyl glycoside. The alkyl glycoside is modified by the following steps:
1) weakly oxidized alkyl glycoside: dissolving an alkyl glycoside solution with the mass fraction of 45% in ethanol, stirring for 5min, adding a Sarett reagent into the solution, wherein the feeding mass ratio of the alkyl glycoside to the Sarett reagent is 0.002: 1, and continuously stirring the solution for 1h until the alkyl glycoside is weakly oxidized; the alkyl glycoside is prepared by the following steps: mixing glucose and octanol according to a molar ratio of 1:1, stirring and heating to 90 ℃, adding benzenesulfonic acid, continuously stirring, wherein the molar ratio of the glucose to the benzenesulfonic acid is 1: 0.1, carrying out acetal dehydration reaction on the glucose and the octanol to generate an alkyl glycoside crude product, removing unreacted octanol through a dealcoholization system, and carrying out decoloration treatment to obtain an alkyl glycoside finished product;
2) nucleophilic addition: adding 35% by mass of formaldehyde aqueous solution into the weak oxidation product obtained in the step 1), wherein the volume ratio of the formaldehyde aqueous solution to the initial alkyl glycoside solution obtained in the step 1) is 1:1, slowly adding 4% NaOH ethanol solution into the solution, wherein the volume ratio of the NaOH ethanol solution to the formaldehyde aqueous solution is 1: 1.5, heating and refluxing, controlling the temperature of the mixed solution at 25 ℃, and fully stirring to ensure that carbanions of the weak oxidation product perform nucleophilic addition on formaldehyde;
3) reduction: adding sodium borohydride powder into the mixture after the nucleophilic addition reaction in the step 2), adding 1.5g of sodium borohydride into every 100ml of alkyl glycoside solution initially selected in the step 1) according to the adding amount of the sodium borohydride powder, stirring the mixture for 3 hours under the cooling condition of ice-water bath, reducing aldehyde ketone into alcohol by the sodium borohydride, purifying the product of the reduction reaction by molecular distillation, and finally obtaining hydroxymethyl alkyl glycoside.
The reaction in the modification process of the alkyl glycoside is as follows:
the method for treating the oily sludge by using the sludge oil removing agent comprises the following steps: selecting oil-containing sludge with 20.0wt% of oil content, 65wt% of water content and 15wt% of mud content in an oil field sludge drying pool, mixing the oil-containing sludge and a sludge oil removing agent according to the mass ratio of 1:3, placing the mixture in a constant-temperature reaction tank, and mixing the oil-containing sludge and the sludge oil removing agent according to the following steps:
1) the mass of the oily sludge to be deoiled is m1According to the mass ratio of the oil-containing sludge to the sludge oil-removing agent of 1:3, calculating the mass m of the sludge oil-removing agent to be prepared2=3 m1According to the components and contents of the sludge oil removal agent, hydroxymethyl alkyl glycoside, peregal, sodium carbonate, potassium pyrophosphate and water are prepared in the same amount;
2) adding the water prepared in the step 1) into a reaction tank, sequentially adding half of the amount of sodium carbonate and all potassium pyrophosphate in the step 1), adding the oily sludge to be deoiled into the reaction tank, and stirring and mixing the solid-liquid mixture added into the reaction tank uniformly;
3) continuously adding the hydroxymethyl alkyl glycoside, peregal and the residual sodium carbonate prepared in the step 1) into the reaction tank in sequence, and uniformly stirring and mixing the oily sludge and the sludge oil removal agent.
Setting the reaction temperature of a reaction tank at 45 ℃ and the stirring speed of 320r/min, fully washing the oily sludge for 1h, standing the mixture in the reaction tank for 2h to ensure that the mixture is sequentially divided into three layers of oil, water and sludge from top to bottom, recovering the oil on the upper layer through a drainage groove on the upper part of the reaction tank, discharging the sludge on the lower layer through a sludge discharge pipe on the lower part of the reaction tank, and testing the oil content of the sludge on the lower layer after oil removal to be 0.28%.
Example 3
In the preparation method of the sludge oil removing agent of the embodiment, the composition and content of the sludge oil removing agent are as follows: hydroxymethyl alkyl glycoside 0.5 wt%; peregal is 0.3 wt%; 5wt% of sodium carbonate; potassium pyrophosphate is 0.1 wt%; the balance of water; the sum of the percentage contents of the components of the sludge oil removing agent is hundred; the hydroxymethyl alkyl glycoside is prepared by modifying alkyl glycoside. The alkyl glycoside is modified by the following steps:
1) weakly oxidized alkyl glycoside: dissolving an alkyl glycoside solution with the mass fraction of 50% in ethanol, stirring for 15min, adding a Sarett reagent into the solution, wherein the feeding mass ratio of the alkyl glycoside to the Sarett reagent is 0.004: 1, and continuously stirring the solution for 3h until the alkyl glycoside is weakly oxidized; the alkyl glycoside is prepared by the following steps: mixing glucose and nonanol according to a molar ratio of 1:20, stirring and heating to 135 ℃, adding benzenesulfonic acid, continuously stirring, carrying out acetal dehydration reaction on the glucose and the nonanol to generate an alkyl glycoside crude product, removing unreacted nonanol by using a dealcoholization system, and carrying out decoloration treatment to obtain an alkyl glycoside finished product;
2) nucleophilic addition: adding 40% by mass of formaldehyde aqueous solution into the weak oxidation product obtained in the step 1), wherein the volume ratio of the formaldehyde aqueous solution to the initial alkyl glycoside solution obtained in the step 1) is 1.33: 1, slowly adding 6% NaOH ethanol solution into the solution, wherein the volume ratio of the NaOH ethanol solution to the formaldehyde aqueous solution is 1:2, heating and refluxing, controlling the temperature of the mixed solution at 35 ℃, and fully stirring to ensure that carbanions of the weak oxidation product perform nucleophilic addition on formaldehyde;
3) reduction: adding sodium borohydride powder into the mixture after the nucleophilic addition reaction in the step 2), adding 1.8g of sodium borohydride into every 100ml of alkyl glycoside solution initially selected in the step 1) according to the adding amount of the sodium borohydride powder, stirring the mixture for 5 hours under the cooling condition of ice-water bath, reducing aldehyde ketone into alcohol by the sodium borohydride, purifying the product of the reduction reaction by molecular distillation, and finally obtaining hydroxymethyl alkyl glycoside.
The reaction in the modification process of the alkyl glycoside is as follows:
the method for treating oily sludge by using the sludge oil removing agent comprises the following steps: selecting oily sludge containing 40wt% of oil, 22wt% of water and 38wt% of mud in an oilfield sludge drying pool, mixing the oily sludge and a sludge oil removing agent according to a mass ratio of 1:4, and placing the mixture in a constant-temperature reaction tank, wherein the oily sludge and the sludge oil removing agent are mixed according to the following steps:
1) the mass of the oily sludge to be deoiled is m1According to the mass ratio of the oil-containing sludge to the sludge oil-removing agent of 1:4, calculating the mass m of the sludge oil-removing agent to be prepared2= 4m1According to the components and contents of the sludge oil removal agent, hydroxymethyl alkyl glycoside, peregal, sodium carbonate, potassium pyrophosphate and water are prepared in the same amount;
2) adding the water prepared in the step 1) into a reaction tank, sequentially adding half of the amount of sodium carbonate and all potassium pyrophosphate in the step 1), adding the oily sludge to be deoiled into the reaction tank, and stirring and mixing the solid-liquid mixture added into the reaction tank uniformly;
3) continuously adding the hydroxymethyl alkyl glycoside, peregal and the residual sodium carbonate prepared in the step 1) into the reaction tank in sequence, and uniformly stirring and mixing the oily sludge and the sludge oil removal agent.
Setting the reaction temperature of a reaction tank at 47 ℃ and the stirring speed of 450r/min, fully washing the oily sludge for 2 hours, standing the mixture in the reaction tank for 3 hours to enable the mixture to be sequentially divided into three layers of oil, water and sludge from top to bottom, recovering the oil on the upper layer through a drainage groove on the upper part of the reaction tank, discharging the sludge on the lower layer through a sludge discharge pipe on the lower part of the reaction tank, and testing the oil content of the sludge on the lower layer after oil removal to be 0.25%.
Example 4
In the preparation method of the sludge oil removing agent of the embodiment, the composition and content of the sludge oil removing agent are as follows: 1 wt% of hydroxymethyl alkyl glycoside; AEO-7 is 1 wt%; 0.1 wt% of sodium carbonate; potassium pyrophosphate 0.06 wt%; the balance of water; the sum of the percentage contents of the components of the sludge oil removing agent is hundred; the hydroxymethyl alkyl glycoside is prepared by modifying alkyl glycoside. The alkyl glycoside is modified by the following steps:
1) weakly oxidized alkyl glycoside: dissolving an alkyl glycoside solution with the mass fraction of 48.5% in ethanol, stirring for 10min, adding a Sarett reagent into the solution, wherein the feeding mass ratio of the alkyl glycoside to the Sarett reagent is 0.003: 1, and continuously stirring the solution for 2h until the alkyl glycoside is weakly oxidized; the alkyl glycoside is prepared by the following steps: mixing glucose and decanol according to a molar ratio of 1:10, stirring and heating to 90 ℃, adding p-toluenesulfonic acid, continuously stirring, wherein the molar ratio of the glucose to the p-toluenesulfonic acid is 1: 0.3, carrying out acetal dehydration reaction on the glucose and the decanol to generate an alkyl glycoside crude product, removing unreacted decanol through a dealcoholization system, and carrying out decoloration treatment to obtain an alkyl glycoside finished product;
2) nucleophilic addition: adding a formaldehyde aqueous solution with the mass fraction of 37% into the weak oxidation product obtained in the step 1), wherein the volume ratio of the formaldehyde aqueous solution to the initial alkyl glycoside solution obtained in the step 1) is 1.2: 1, slowly adding a NaOH ethanol solution with the concentration of 5% into the solution, wherein the volume ratio of the NaOH ethanol solution to the formaldehyde aqueous solution is 1:2, heating and refluxing, controlling the temperature of the mixed solution at 30 ℃, and fully stirring to ensure that carbanions of the weak oxidation product perform nucleophilic addition on formaldehyde;
3) adding sodium borohydride powder into the mixture after the nucleophilic addition reaction in the step 2), adding 1.53g of sodium borohydride into every 100ml of alkyl glycoside solution initially selected in the step 1) according to the adding amount of the sodium borohydride powder, stirring the mixture for 5 hours under the cooling condition of an ice-water bath, reducing aldehyde ketone into alcohol by the sodium borohydride, purifying the product of the column chromatography reduction reaction, and finally obtaining the hydroxymethyl alkyl glycoside.
The reaction in the modification process of the alkyl glycoside is as follows:
the method for treating oily sludge by using the sludge oil removing agent comprises the following steps: selecting oil-containing sludge containing 57wt% of oil, 20wt% of water and 23wt% of mud in an oil field sludge drying pool, mixing the oil-containing sludge and a sludge oil removing agent according to a mass ratio of 1:4, placing the mixture in a constant-temperature reaction tank, and mixing the oil-containing sludge and the sludge oil removing agent according to the following steps:
1) the mass of the oily sludge to be deoiled is m1According to the mass ratio of the oil-containing sludge to the sludge oil-removing agent of 1:4, calculating the mass m of the sludge oil-removing agent to be prepared2=4 m1According to the components and the content of the sludge oil removing agent, hydroxymethyl alkyl glycoside, AEO-7, sodium carbonate, potassium pyrophosphate and water are prepared in the same application amount;
2) adding the water prepared in the step 1) into a reaction tank, sequentially adding half of the amount of sodium carbonate and all potassium pyrophosphate in the step 1), adding the oily sludge to be deoiled into the reaction tank, and stirring and mixing the solid-liquid mixture added into the reaction tank uniformly;
3) continuously adding the hydroxymethyl alkyl glycoside prepared in the step 1), AEO-7 and the residual sodium carbonate into the reaction tank in sequence, and uniformly stirring and mixing the oily sludge and the sludge oil removal agent.
Setting the reaction temperature of a reaction tank at 45 ℃ and the stirring speed of 400r/min, fully washing the oily sludge for 2 hours, standing the mixture in the reaction tank for 3 hours to enable the mixture to be sequentially divided into three layers of oil, water and sludge from top to bottom, recovering the oil on the upper layer through a drainage groove on the upper part of the reaction tank, discharging the sludge on the lower layer through a sludge discharge pipe on the lower part of the reaction tank, and testing the oil content of the sludge on the lower layer after oil removal to be 0.05%.
The method comprises the steps of keeping the content of AEO-7 or peregal, the content of sodium carbonate and the content of potassium pyrophosphate in a sludge oil removal agent to be 1 wt%, 5wt% and 0.1 wt% respectively, preparing sludge oil removal agents with different hydroxymethyl alkyl glycoside concentrations, treating field oil-containing sludge of a sludge drying pool of an oil field, wherein the content of oil in the sludge is 57wt%, the content of argillaceous substances is 43 wt%, and the mass ratio of the sludge oil removal agent to the oil-containing sludge is 4:1, wherein the treatment results are shown in the following table.
The table shows that the oil removing effect of the sludge oil removing agent added with hydroxymethyl alkyl glycoside is further enhanced, and the oil content in the sludge after oil removal is lower than 0.3%; with the increase of the concentration of the hydroxymethyl alkyl glycoside, the oil removing effect of the sludge oil removing agent becomes better, and the oil content in the oil-removed sludge is lower; the oil in the oily sludge can be more thoroughly separated by hydroxymethyl alkyl glycoside.
The present invention is not limited to the above-mentioned embodiments, and based on the technical solutions disclosed in the present invention, those skilled in the art can make some substitutions and modifications to some technical features without creative efforts according to the disclosed technical contents, and these substitutions and modifications are all within the protection scope of the present invention.
Claims (8)
1. The preparation method of the sludge oil removing agent is characterized in that the sludge oil removing agent comprises the following components in percentage by weight: 0.1-1 wt% of hydroxymethyl alkyl glycoside; AEO-7 or peregal is 0.1-1 wt%; 0.1-5 wt% of sodium carbonate; potassium pyrophosphate in an amount of 0.01 to 0.1 wt%; the balance of water; the sum of the percentage contents of the components of the sludge oil removing agent is hundred; the hydroxymethyl alkyl glycoside is prepared by modifying alkyl glycoside, and the reaction in the alkyl glycoside modification process is as follows:
2. the method for preparing the agent for removing oil from sludge according to claim 1, wherein the alkyl glycoside is modified by the following steps:
1) weakly oxidized alkyl glycoside: dissolving an alkyl glycoside solution with the mass fraction of 45-50% in ethanol, stirring for 5-15 min, adding a Sarett reagent into the solution, wherein the volume ratio of the alkyl glycoside solution to the ethanol is 1: 1.5-1.8, and the feeding mass ratio of the alkyl glycoside to the Sarett reagent is (0.002-0.004): 1, and continuously stirring the solution for 1-3 h until the alkyl glycoside is weakly oxidized;
2) nucleophilic addition: adding 35-40% of formaldehyde aqueous solution into the weak oxidation product obtained in the step 1), wherein the volume ratio of the formaldehyde aqueous solution to the initial alkyl glycoside solution obtained in the step 1) is (1-1.33) to 1, slowly adding 4-6% of NaOH ethanol solution into the solution, wherein the volume ratio of the NaOH ethanol solution to the formaldehyde aqueous solution is 1 to (1.5-2), heating and refluxing, controlling the temperature of the mixed solution at 25-35 ℃, and fully stirring to ensure that carbanions of the weak oxidation product perform nucleophilic addition on formaldehyde;
3) reduction: adding sodium borohydride powder into the mixture obtained after the nucleophilic addition reaction in the step 2), adding 1.5-1.8 g of sodium borohydride into every 100ml of alkyl glycoside solution initially selected in the step 1), stirring the mixture for 3-5 hours under the cooling condition of ice-water bath, reducing aldehyde ketone into alcohol by using the sodium borohydride, purifying the product of the reduction reaction, and finally obtaining hydroxymethyl alkyl glycoside.
3. The method for preparing the agent for removing oil from sludge according to claim 2, wherein the alkyl glycoside in the step 1) is prepared by the following steps: mixing glucose and long-chain alkyl alcohol according to a molar ratio of 1 (1-20), stirring and heating to 45-135 ℃, adding an acid catalyst, continuously stirring, wherein the molar ratio of the glucose to the acid catalyst is 1 (0.1-0.5), carrying out acetal dehydration reaction on the glucose and the long-chain alkyl alcohol to generate an alkyl glycoside crude product, removing unreacted long-chain alkyl alcohol through a dealcoholization system, and carrying out decoloration treatment to obtain an alkyl glycoside finished product.
4. The method for preparing an agent for removing oil from sludge according to claim 3, wherein the long-chain alkyl alcohol is hexanol, octanol, nonanol or decanol.
5. The method for preparing a sludge oil removing agent as claimed in claim 3, wherein the acidic catalyst is p-toluenesulfonic acid or benzenesulfonic acid.
6. The method for preparing a sludge degreasing agent as claimed in claim 2, wherein the hydroxymethyl alkyl glycoside is purified in step 3) by column chromatography or molecular distillation.
7. The use method of the sludge degreasing agent as claimed in claim 1, characterized by comprising the following steps:
mixing oil-containing sludge and a sludge oil removing agent according to a mass ratio of 1 (2-4), placing the mixture into a constant-temperature reaction tank, setting the reaction temperature of the reaction tank to be 45-50 ℃, and the stirring speed to be 200-450 r/min, fully washing the oil-containing sludge for 1-2 h, standing the mixture in the reaction tank for 1-3 h, sequentially dividing the mixture into three layers of oil, water and sludge from top to bottom, recovering the oil on the upper layer through a drainage groove on the upper part of the reaction tank, and discharging the sludge on the lower layer through a sludge discharge pipe on the lower part of the reaction tank to remove the oil in the oil-containing sludge.
8. The method for using the agent for removing oil from sludge as claimed in claim 7, wherein the oil-containing sludge and the agent for removing oil from sludge are mixed by the following steps:
1) the mass of the oily sludge to be deoiled is m1According to the mass ratio of the oily sludge to the sludge oil-removing agent being 1 (2-4), calculating the mass m of the sludge oil-removing agent to be prepared2According to the components and contents of the sludge oil removing agent, hydroxymethyl alkyl glycoside, AEO-7 or peregal, sodium carbonate, potassium pyrophosphate and water are prepared in the same amount;
2) adding the water prepared in the step 1) into a reaction tank, sequentially adding half of the amount of sodium carbonate and all potassium pyrophosphate in the step 1), adding the oily sludge to be deoiled into the reaction tank, and stirring and mixing the solid-liquid mixture added into the reaction tank uniformly;
3) continuously adding the hydroxymethyl alkyl glycoside, AEO-7 or peregal prepared in the step 1) and the residual sodium carbonate into the reaction tank in sequence, and uniformly stirring and mixing the oily sludge and the sludge oil removal agent.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996003412A1 (en) * | 1994-07-22 | 1996-02-08 | Henkel Corporation | Process for making alkyl polyglycosides |
| JP4167919B2 (en) * | 2003-03-27 | 2008-10-22 | ハイモ株式会社 | Sludge dewatering method |
| CN104342327A (en) * | 2013-08-08 | 2015-02-11 | 厦门泰益新洁净科技有限公司 | Oil-stain cleaning agent as well as preparation method and use method thereof |
| CN104710089A (en) * | 2015-03-23 | 2015-06-17 | 东营金岛环境工程有限公司 | Oily sludge dehydration technology |
| CN105418697A (en) * | 2015-11-02 | 2016-03-23 | 中国石油天然气股份有限公司 | Alkyl polyglucoside sulfonate surfactant, preparation method therefor and application of alkyl polyglucoside sulfonate surfactant |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US5006239A (en) * | 1986-11-20 | 1991-04-09 | Tetra Technologies, Inc. | apparatus for treatment of oily sludge |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996003412A1 (en) * | 1994-07-22 | 1996-02-08 | Henkel Corporation | Process for making alkyl polyglycosides |
| JP4167919B2 (en) * | 2003-03-27 | 2008-10-22 | ハイモ株式会社 | Sludge dewatering method |
| CN104342327A (en) * | 2013-08-08 | 2015-02-11 | 厦门泰益新洁净科技有限公司 | Oil-stain cleaning agent as well as preparation method and use method thereof |
| CN104710089A (en) * | 2015-03-23 | 2015-06-17 | 东营金岛环境工程有限公司 | Oily sludge dehydration technology |
| CN105418697A (en) * | 2015-11-02 | 2016-03-23 | 中国石油天然气股份有限公司 | Alkyl polyglucoside sulfonate surfactant, preparation method therefor and application of alkyl polyglucoside sulfonate surfactant |
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