CN112391190A - CO2/N2Switch type double-circulation extraction process and application thereof - Google Patents
CO2/N2Switch type double-circulation extraction process and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/04—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction
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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
Abstract
The invention discloses CO2/N2The switch type double-circulation extraction process is characterized in that oil-containing solid waste and organic acid are mixed and separated to obtain mixed liquor A and solid waste; adding the polyether amine aqueous solution into the mixed solution A to separate to obtain an oil phase and a mixed solution B, and introducing CO into the mixed solution B2Separating after protonation to obtain organic acid and mixed liquor C, returning the organic acid into the oil-containing solid waste, introducing N into the mixed liquor C2Deprotonation to give CO2And the aqueous solution of the polyether amine returns to the mixed solution A, CO2Returning the mixture to the mixed solution B, wherein the temperature control range of the whole extraction process is 30-70 ℃; (1) the organic acid and the polyether amine aqueous solution are combined for use, so that the purpose of oil removal is achieved, the organic acid and the polyether amine aqueous solution are recycled, the environment is protected, the operation is safe, and the oil removal cost is saved; the recovery rate of the oil product is higher, other impurities are not introduced, and the conventional oil product is specialThe recovery rate of heavy oil products can reach more than 90 percent.
Description
Technical Field
The invention belongs to the technical field of oil-containing solid waste cleaning, and particularly relates to CO2/N2A switch type double-circulation extraction process and application thereof in cleaning oil-containing solid waste.
Background
The traditional cleaning process of the oil-containing solid waste mainly takes oil-soluble tertiary amine as a main part, as shown in figure 1, the oil-soluble tertiary amine is used for dissolving oil substances in the oil-containing solid waste, and residues are separated; adding water into the mixed system of the dissolved oil and introducing CO2Protonating oil-soluble tertiary amine, and allowing the oil-soluble tertiary amine to enter a water phase from an oil phase to form an ammonium salt solution; recovering oil substances in a liquid separation mode; introducing N into the ammonium salt solution2Deprotonating, converting ammonium salt into oil-soluble tertiary amine, separating the oil-soluble tertiary amine from a water phase, and removing water to obtain the oil-soluble tertiary amine for recycling; because the oil-soluble tertiary amine is easy to volatilize, has high toxicity, low flash point, flammability and explosiveness and the like, the traditional oil-containing solid waste cleaning process is difficult to realize industrialization and has narrow application range.
Disclosure of Invention
Aiming at the problems of the traditional oil-containing solid waste cleaning process, the invention provides CO2/N2Switch type double circulation extraction process.
The technical scheme of the invention is as follows: CO (carbon monoxide)2/N2The switch type double-circulation extraction process is characterized in that oil-containing solid waste and organic acid are mixed and separated to obtain mixed liquor A and solid waste; adding the polyether amine aqueous solution into the mixed solution A to separate to obtain an oil phase and a mixed solution B, and introducing CO into the mixed solution B2Separating after protonation to obtain organic acid and mixed liquor C, returning the organic acid into the oil-containing solid waste, introducing N into the mixed liquor C2Deprotonation to give CO2And the aqueous solution of the polyether amine returns to the mixed solution A, CO2Returning to the mixed solution B, and controlling the temperature of the whole extraction process within the range of 30-70 ℃.
The invention has the beneficial effects that: the organic acid and the polyether amine are both recyclable, no waste liquid is generated, the environment is protected, the use of reagents is reduced, and the economic effect is good; the oil product obtained by adopting the organic acid for extraction has high purity, the demulsification can be realized by only heating the oil-in-water emulsion formed in the recovery process of the organic acid, the heating temperature is low, the demulsification effect is good, and the recovery rate of the oil product is high.
(1) The organic acid and the polyether amine aqueous solution are combined for use, so that the purpose of oil removal is achieved, the organic acid and the polyether amine aqueous solution are recycled, the environment is protected, the operation is safe, and the oil removal cost is saved; (2) the organic acid has the advantages of good biocompatibility, weak volatility, high flash point and low flammable and explosive risks; (3) the low-cost, environment-friendly and biodegradable polyether amine is used for replacing oil-soluble tertiary amine which has high cost, high toxicity, easy volatilization, flammability and explosiveness.
The recovery rate of the oil product is high, other impurities are not introduced, and the recovery rate of the conventional oil product, particularly the heavy oil product, can reach more than 90 percent.
The organic acid is directly contacted with the oil in the oil-containing solid waste, mutual solubility can be realized at normal temperature, and the recovery rate of the oil product is more than 90 percent.
Further limiting, the organic acid is one or a mixture of more of fatty acids with 10-14 carbon atoms;
or one or more mixtures of C8-16 olefine acids.
The invention has the beneficial effects that: selecting C10-C14Of C chain length or C8-C16The reason for the C chain length of alkenoic acid (a): a certain carbon chain length is required to ensure the oil solubility of fatty acid or olefine acid so as to achieve a better oil extraction effect; the extraction temperature of the fatty acid or the olefine acid with the longer C chain can be influenced by the self melting point, and the stability of the system can be influenced when the extraction temperature approaches the boiling point of water; the olefine acid has unsaturated bonds, so compared with fatty acid and naphthenic acid which have the same number of carbon atoms, the olefine acid has the lowest melting point and needs low heating temperature, and the energy consumption in the olefine acid separation process is reduced.
The temperature control range of the whole process is 30-70 ℃, the organic acid and the mixed solution B are easy to demulsify and obvious in phase splitting, the organic acid can be recovered by adopting a conventional liquid separation method, only trace O/W emulsion is generated, and no oil product residue exists in a circulating system through conventional liquid separation operation, so that the circulating recycling of a subsequent system is not hindered; the method is favorable for protonating polyether amine to obtain ammonium bicarbonate, organic acid cannot flocculate, molecular diffusion can be accelerated, and the system phase splitting phenomenon is more obvious; and is also beneficial to deprotonating ammonium bicarbonate to obtain polyether amine; in the extraction process, the polyether amine is not directly contacted with the solid residue, and no residue is left on the surface of the solid residue; the organic acid and the solid residue have the same charge tendency, and the organic acid and the solid residue are repelled by static electricity, so that the solid-liquid separation effect is improved; the whole circulation separation process is simple liquid separation and filtration, no separation steps with large energy consumption such as water removal and the like are adopted, energy consumption is saved, and the recovery rate of the polyetheramine aqueous solution and the organic acid is high.
Further defined, the polyetheramine is polyetheramine D230 or polyetheramine D400.
Further limiting, the organic acid is n-decanoic acid, the polyether amine is polyether amine D230, and the temperature control range of the whole extraction process is 30-38 DEG C
Further limiting, the organic acid is lauric acid, the polyether amine is polyether amine D230, and the temperature control range of the whole extraction process is 55-67 ℃.
Further limiting, the organic acid is myristic acid, the polyether amine is polyether amine D230, and the temperature control range of the whole extraction process is 63-70 ℃.
Further limiting, the organic acid is undecylenic acid, the polyether amine is polyether amine D230, and the temperature control range of the whole extraction process is 33-37 ℃.
Further defined, the concentration of the polyether amine in the polyether amine aqueous solution is 0.5-23 wt%, and the molar amount of the organic acid is 2 times of that of the polyether amine.
The invention also discloses CO2/N2The application of the switch type double-circulation extraction oil system reagent in cleaning oil-containing solid waste; the oil-containing solid waste is refined sludge.
Drawings
FIG. 1 is a flow chart of a traditional oil-containing solid waste cleaning process;
FIG. 2 is a flow diagram of a simulated oil dual cycle extraction process;
FIG. 3 is a flow diagram of a refinery sludge dual cycle extraction process;
FIG. 4 is CO2/N2Working principle diagram of switch type double-circulation extraction oil system；
FIG. 5 is CO with deionized water/polyetheramine D230/n-decanoic acid as solvent2/N2A first cycle process diagram of a switch type double-cycle extraction oil system;
FIG. 6 is CO with DI water/polyetheramine D230/n-decanoic acid as solvent2/N2A second cycle process diagram of the switch type double-cycle extraction oil system;
FIG. 7 is CO with DI water/polyetheramine D400/n-decanoic acid as solvent2/N2A first cycle process diagram of a switch type double-cycle extraction oil system;
FIG. 8 shows CO in DI water/polyetheramine D400/n-decanoic acid as solvent2/N2A second cycle process diagram of the switch type double-cycle extraction oil system;
FIG. 9 is CO with DI water/polyetheramine D230/n-decanoic acid as solvent2/N2A cycle process diagram of a switch type double-cycle dodecane extraction system;
FIG. 10 shows CO in DI water/polyetheramine D230/n-decanoic acid as solvent2/N2A process diagram of a switch type double-circulation white oil extraction system;
FIG. 11 is CO with DI water/polyetheramine D230/n-decanoic acid as solvent2/N2A process diagram of a switch type double-circulation extraction kerosene system.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the embodiments of the present invention are described in detail and completely, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It will be understood by those skilled in the art that, unless otherwise defined, all terms (including 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. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the prior art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
The oil-containing solid waste is refined sludge, and a double-circulation extraction process is established, as shown in figure 3.
CO2/N2The working principle of the switch type double-circulation extraction oil system reagent is shown in figure 4, organic acid and polyetheramine aqueous solution react to generate organic acid ammonium salt aqueous solution; introducing CO2The organic acid ammonium salt is protonated, and the organic acid is directly separated from the water phase (ammonium bicarbonate salt solution); introducing N into the water phase2(CO is discharged)2) Deprotonating ammonium bicarbonate salt to obtain the polyether amine aqueous solution again, and directly entering the next cycle by using both organic acid and the polyether amine aqueous solution.
CO (carbon monoxide)2/N2The switch type double-circulation extraction process is characterized in that oil-containing solid waste and organic acid are mixed and separated to obtain mixed liquor A and solid waste; adding the polyether amine aqueous solution into the mixed solution A to separate to obtain an oil phase and a mixed solution B, and introducing CO into the mixed solution B2Separating after protonation to obtain organic acid and mixed liquor C, returning the organic acid into the oil-containing solid waste, introducing N into the mixed liquor C2Deprotonation to give CO2And the aqueous solution of the polyether amine returns to the mixed solution A, CO2Returning to the mixed solution B, and controlling the temperature of the whole extraction process within the range of 30-70 ℃.
The organic acid is one or a mixture of more of fatty acids with 10-14 carbon atoms; or one or more mixtures of C8-16 olefine acids; wherein the fatty acid can be n-capric acid, lauric acid and myristic acid, and the olefinic acid can be undecylenic acid, dodecenoic acid and arachidonic acid; the molecular formula of the n-decanoic acid is: c10H20O2The structural formula is as follows:
the molecular weight is 172.26, and the optimal temperature range is 30-38 ℃; the molecular formula of lauric acid is: c12H24O2The structural formula is as follows:
the molecular weight is 200.32, and the optimal temperature range is 55-67 ℃; the molecular formula of myristic acid is: c14H28O2The structural formula is as follows:
the molecular weight is 228.38, and the optimal temperature range is 63-70 ℃; the n-decanoic acid, lauric acid, myristic acid, undecylene, dodecenoic acid, and arachidonic acid are all commercially available as they are.
The polyether amine is polyether amine D230 or polyether amine D400, and the structural formula of the polyether amine D400 is as follows:
polyetheramine D230 or polyetheramine D400 can be obtained directly from the market.
8 organic acid reacts with the polyether amine water solution by adopting CO2Protonation and N2The effect of deprotonation was tested as follows:
test example 1
The drugs used in this test example were: 50ml of deionized water, 0.5g of polyetheramine D230 and 0.749g of n-decanoic acid, as shown in FIG. 5,
step S1: placing the beaker in a hot water bath, wherein the temperature of the hot water bath is 65 ℃, adding polyetheramine D230 and deionized water into the beaker, then adding n-decanoic acid into the beaker, and simultaneously carrying out magnetic stirring continuously to obtain a mixed solution;
step S2: introducing CO into the mixed solution2Protonating while magnetic stirring, clarifying, and introducing N2Deprotonating and continuously performing magnetic stirring at the same time, and observing the turbidity condition of the solution;
a second cycle is established, as shown in figure 6,
introducing CO into the solution finally obtained in the step S22Protonating while magnetic stirring, standing for clarification, and introducing N2Deprotonation and continuous magnetic stirring are carried out at the same time,the solution was observed for turbidity.
In this test example, CO was introduced2The n-decanoic acid is not separated after protonation, and the n-decanoic acid directly reacts with the deprotonated and reduced polyetheramine to form a clear solution, so that the deprotonation performance of the ammonium bicarbonate salt solution can be conveniently observed.
Test example 2
The drugs used in this test example were: 50ml of deionized water, 0.5g of polyetheramine D400 and 0.431g of n-decanoic acid, as shown in FIG. 7,
step S1: placing the beaker in a hot water bath, wherein the temperature of the hot water bath is 65 ℃, adding polyetheramine D400 and deionized water into the beaker, then adding n-decanoic acid into the beaker, and simultaneously carrying out magnetic stirring continuously to obtain a mixed solution;
step S2: introducing CO into the mixed solution2Protonating while magnetic stirring, clarifying, and introducing N2Deprotonating and continuously performing magnetic stirring at the same time, and observing the turbidity condition of the solution;
a second cycle is established, as shown in figure 8,
introducing CO into the solution finally obtained in the step S22Protonating while magnetic stirring, standing for clarification, and introducing N2Deprotonation was carried out while magnetic stirring was continued, and the turbidity of the solution was observed.
In this test example, CO was introduced2The n-decanoic acid is not separated after protonation, and the n-decanoic acid directly reacts with the deprotonated and reduced polyetheramine to form a clear solution, so that the deprotonation performance of the ammonium bicarbonate salt solution can be conveniently observed.
In test examples 1 and 2, CO was introduced215 seconds, the double circulation system obviously generates an emulsification effect, and proves that the n-capric acid is quickly protonated and has good protonation performance;
according to the test example 1 and the test example 2, the n-decanoic acid and the ammonium bicarbonate salt solution are easy to demulsify and obvious in phase separation at 65 ℃, and the organic acid can be recovered by adopting a conventional liquid separation method. N is a radical of2Deprotonation is rapid and N is bubbled with stirring at 65 ℃2And is clear after 0.5 h.
Example 1
The drugs of this example are: 50ml of deionized water +0.5g of polyetheramine D230+0.749g of n-decanoic acid +20ml of dodecane;
in this example, dodecane was used to replace the oil-containing solid waste to establish a dual-cycle extraction process, as shown in fig. 9;
step S1: mixing 50ml of deionized water and 0.5g of polyetheramine D230 to obtain a polyetheramine D230 aqueous solution;
step S2: placing dodecane in a beaker, placing the beaker in a hot water bath at the temperature of 50 ℃, and adding n-decanoic acid into the beaker while continuously performing magnetic stirring;
step S3: adding the polyetheramine D230 aqueous solution and continuously carrying out magnetic stirring is more favorable for leading the reaction system to react completely to achieve clear ammonium n-decanoate solution and oil phase, wherein the upper layer is the oil phase, and the lower layer is the ammonium n-decanoate solution;
step S4: separating to obtain a clear ammonium n-decanoate solution and an upper layer liquid, wherein the upper layer liquid after standing comprises the following components: 18.1ml of a clear oil and 3ml of a white emulsion, the white emulsion being an O/W emulsion (oil-in-water emulsion), by heating or by introducing CO2The method can accelerate the demulsification of the white emulsion to obtain separated oil phase and water phase;
introducing CO into the clarified ammonium n-decanoate solution2Protonating to obtain an ammonium bicarbonate solution and n-capric acid, separating to obtain the ammonium bicarbonate solution, and returning the n-capric acid to the step S2, wherein the process is carried out in a hot water bath at the temperature of 30 ℃;
step S5: introducing N into the ammonium bicarbonate solution2Deprotonation to obtain polyetheramine D230 aqueous solution and CO2，CO2Returning to step S4, the aqueous solution of polyetheramine D230 is returned to step S3, the process is carried out in a hot water bath, the temperature of which is 30 ℃;
the calculated recovery of the oil phase (dodecane) was greater than 90.5%.
Example 2
The drugs used in this example were: 50ml of deionized water, 0.5g of polyetheramine D230, 0.749g of n-decanoic acid and 20ml of white oil;
in this example, white oil was used to replace solid waste containing oil, and a dual cycle extraction process was established, as shown in fig. 10;
step S1: mixing 50ml of deionized water and 0.5g of polyetheramine D230 to obtain a polyetheramine D230 aqueous solution;
step S2: placing the white oil in a beaker, placing the beaker in a hot water bath at the temperature of 32 ℃, and adding n-decanoic acid into the beaker while continuously performing magnetic stirring;
step S3: adding the polyetheramine D230 aqueous solution and continuously carrying out magnetic stirring is more favorable for leading the reaction system to react completely to achieve clear ammonium n-decanoate solution and oil phase, wherein the upper layer is the oil phase, and the lower layer is the ammonium n-decanoate solution;
step S4: separating to obtain a clear ammonium n-decanoate solution and an upper layer liquid, wherein the upper layer liquid after standing comprises the following components: 18.8ml of a clear oil, 0.2ml of a white emulsion, which is an O/W emulsion (oil-in-water emulsion), and 3ml of an ammonium n-decanoate solution, by heating or by introducing CO2The method can accelerate the demulsification of the white emulsion to obtain separated oil phase and water phase;
introducing CO into the clarified ammonium n-decanoate solution2Protonating to obtain an ammonium bicarbonate solution and n-capric acid, separating to obtain the ammonium bicarbonate solution, and returning the n-capric acid to the step S2, wherein the process is carried out in a hot water bath at the temperature of 32 ℃;
step S5: introducing N into the ammonium bicarbonate solution2Deprotonation to obtain polyetheramine D230 aqueous solution and CO2，CO2Returning to step S4, the aqueous solution of polyetheramine D230 is returned to step S3, the process is carried out in a hot water bath at a temperature of 32 ℃;
the calculated recovery of the oil phase (white oil) was 94%.
Example 3
The drugs used in this example were: 50ml of deionized water +0.5g of polyetheramine D230+0.749g of n-decanoic acid +20ml of kerosene;
in this embodiment, kerosene is used to replace oil-containing solid waste, and a dual-cycle extraction process is established, as shown in fig. 11;
step S1: mixing 50ml of deionized water and 0.5g of polyetheramine D230 to obtain a polyetheramine D230 aqueous solution;
step S2: placing the white oil in a beaker, placing the beaker in a hot water bath at the temperature of 38 ℃, and adding n-decanoic acid into the beaker while continuously performing magnetic stirring;
step S3: adding the polyetheramine D230 aqueous solution and continuously carrying out magnetic stirring is more favorable for leading the reaction system to react completely to achieve clear ammonium n-decanoate solution and oil phase, wherein the upper layer is the oil phase, and the lower layer is the ammonium n-decanoate solution;
step S4: separating to obtain a clear ammonium n-decanoate solution and an upper layer liquid, wherein the upper layer liquid after standing comprises the following components: 18ml of a clear oil, 0.2ml of a white emulsion, which is an O/W emulsion (oil-in-water emulsion), and 4.6ml of an ammonium n-decanoate solution, by heating or by introducing CO2The method can accelerate the demulsification of the white emulsion to obtain separated oil phase and water phase;
introducing CO into the clarified ammonium n-decanoate solution2Protonating to obtain an ammonium bicarbonate solution and n-capric acid, separating to obtain the ammonium bicarbonate solution, and returning the n-capric acid to the step S2, wherein the process is carried out in a hot water bath at the temperature of 38 ℃;
step S5: introducing N into the ammonium bicarbonate solution2Deprotonation to obtain polyetheramine D230 aqueous solution and CO2，CO2Returning to step S4, the aqueous solution of polyetheramine D230 is returned to step S3, the process is carried out in a hot water bath, the temperature of which is 38 ℃;
the recovery of oil phase (kerosene) was calculated to be 90%.
Example 4
The drugs used in this example were: 50ml of deionized water +0.5g of polyetheramine D230+0.723g of lauric acid +20ml of kerosene;
in this embodiment, kerosene is used to replace oil-containing solid waste, and a dual-cycle extraction process is established, as shown in fig. 11;
step S1: mixing 50ml of deionized water and 0.5g of polyetheramine D230 to obtain a polyetheramine D230 aqueous solution;
step S2: placing white oil in a beaker, placing the beaker in a hot water bath at the temperature of 67 ℃, adding lauric acid in the beaker, and simultaneously and continuously performing magnetic stirring;
step S3: adding the polyetheramine D230 aqueous solution and continuously carrying out magnetic stirring is more favorable for enabling the reaction system to completely react to obtain clear ammonium laurate solution and oil phase, wherein the upper layer is the oil phase, and the lower layer is the ammonium laurate solution;
step S4: separating to obtain a clear lauric acid ammonium salt solution and an upper layer liquid, wherein the upper layer liquid after standing comprises the following components: 18.4ml of a clear oil, 0.2ml of a white emulsion, which is an O/W emulsion (oil-in-water emulsion), and 4.6ml of an ammonium laurate solution, by heating or by introducing CO2The method can accelerate the demulsification of the white emulsion to obtain separated oil phase and water phase;
introducing CO into the clarified ammonium laurate solution2Protonating to obtain an ammonium bicarbonate solution and lauric acid, separating to obtain the ammonium bicarbonate solution, and returning the lauric acid to the step S2, wherein the process is carried out in a hot water bath at the temperature of 67 ℃;
step S5: introducing N into the ammonium bicarbonate solution2Deprotonation to obtain polyetheramine D230 aqueous solution and CO2，CO2Returning to step S4, the aqueous solution of polyetheramine D230 is returned to step S3, the process is carried out in a hot water bath, the temperature of which is 67 ℃;
the recovery of oil phase (kerosene) was calculated to be 92%.
Example 5
The drugs used in this example were: 50ml of deionized water +0.5g of polyetheramine D230+0.723g of lauric acid +20ml of kerosene;
in this embodiment, kerosene is used to replace oil-containing solid waste, and a dual-cycle extraction process is established, as shown in fig. 11;
step S1: mixing 50ml of deionized water and 0.5g of polyetheramine D230 to obtain a polyetheramine D230 aqueous solution;
step S2: placing white oil in a beaker, placing the beaker in a hot water bath at the temperature of 62 ℃, adding lauric acid in the beaker, and simultaneously and continuously performing magnetic stirring;
step S3: adding the polyetheramine D230 aqueous solution and continuously carrying out magnetic stirring is more favorable for enabling the reaction system to completely react to obtain clear ammonium laurate solution and oil phase, wherein the upper layer is the oil phase, and the lower layer is the ammonium laurate solution;
step S4: separating to obtain a clear lauric acid ammonium salt solution and an upper layer liquid, wherein the upper layer liquid after standing comprises the following components: 18.4ml of a clear oil, 0.2ml of a white emulsion, which is an O/W emulsion (oil-in-water emulsion), and 4.6ml of an ammonium laurate solution, by heating or by introducing CO2The method can accelerate the demulsification of the white emulsion to obtain separated oil phase and water phase;
introducing CO into the clarified ammonium laurate solution2Protonating to obtain an ammonium bicarbonate solution and lauric acid, separating to obtain the ammonium bicarbonate solution, and returning the lauric acid to the step S2, wherein the process is carried out in a hot water bath at the temperature of 62 ℃;
step S5: introducing N into the ammonium bicarbonate solution2Deprotonation to obtain polyetheramine D230 aqueous solution and CO2，CO2Returning to step S4, the aqueous solution of polyetheramine D230 is returned to step S3, the process is carried out in a hot water bath, the temperature of which is 62 ℃;
the recovery of oil phase (kerosene) was calculated to be 92%.
Example 6
The drugs used in this example were: 50ml of deionized water +0.5g of polyetheramine D230+0.784g of myristic acid +20ml of kerosene;
in this embodiment, kerosene is used to replace oil-containing solid waste, and a dual-cycle extraction process is established, as shown in fig. 11;
step S1: mixing 50ml of deionized water and 0.5g of polyetheramine D230 to obtain a polyetheramine D230 aqueous solution;
step S2: putting white oil into a beaker, putting the beaker into a hot water bath at the temperature of 65 ℃, and adding myristic acid into the beaker while continuously performing magnetic stirring;
step S3: adding the polyetheramine D230 aqueous solution and continuously carrying out magnetic stirring is more favorable for ensuring that the reaction system completely reacts to achieve clear ammonium myristate solution and oil phase, wherein the upper layer is the oil phase, and the lower layer is the ammonium myristate solution;
step S4: separating to obtain clear ammonium myristate solution and upper liquid, wherein the upper liquid after standing comprises the following components: 18.9ml of a clear oil, 0.2ml of a white emulsion, which is an O/W emulsion (oil-in-water emulsion), and 4.6ml of an ammonium myristate salt solution by heating or by passing CO through2The method can accelerate the demulsification of the white emulsion to obtain separated oil phase and water phase;
introducing CO into the clarified ammonium myristate solution2Protonating to obtain an ammonium bicarbonate solution and lauric acid, separating to obtain the ammonium bicarbonate solution, and returning myristic acid to the step S2, wherein the process is carried out in a hot water bath at the temperature of 65 ℃;
step S5: introducing N into the ammonium bicarbonate solution2Deprotonation to obtain polyetheramine D230 aqueous solution and CO2，CO2Returning to step S4, the aqueous solution of polyetheramine D230 is returned to step S3, the process is carried out in a hot water bath, the temperature of which is 65 ℃;
the recovery of oil phase (kerosene) was calculated to be 94.5%.
Example 7
The drugs used in this example were: 50ml of deionized water +0.5g of polyetheramine D400+0.784g of myristic acid +20ml of kerosene;
in this embodiment, kerosene is used to replace oil-containing solid waste, and a dual-cycle extraction process is established, as shown in fig. 11;
step S1: mixing 50ml of deionized water and 0.5g of polyetheramine D400 to obtain a polyetheramine D400 aqueous solution;
step S2: putting white oil into a beaker, putting the beaker into a hot water bath at the temperature of 65 ℃, and adding myristic acid into the beaker while continuously performing magnetic stirring;
step S3: adding the polyetheramine D400 aqueous solution and continuously carrying out magnetic stirring is more favorable for ensuring that the reaction system completely reacts to achieve clear ammonium myristate solution and oil phase, wherein the upper layer is the oil phase, and the lower layer is the ammonium myristate solution;
step S4: separating to obtain clear ammonium myristate solution and upper liquid, wherein the upper liquid after standing comprises the following components: 19ml ofClear oil, 0.2ml of white emulsion and 4.6ml of ammonium myristate solution, wherein the white emulsion is O/W emulsion (oil-in-water emulsion), by heating or introducing CO2The method can accelerate the demulsification of the white emulsion to obtain separated oil phase and water phase;
introducing CO into the clarified ammonium myristate solution2Protonating to obtain an ammonium bicarbonate solution and lauric acid, separating to obtain the ammonium bicarbonate solution, and returning myristic acid to the step S2, wherein the process is carried out in a hot water bath at the temperature of 65 ℃;
step S5: introducing N into the ammonium bicarbonate solution2Deprotonation to obtain polyetheramine D400 aqueous solution and CO2，CO2Returning to step S4, the polyetheramine D400 aqueous solution returns to step S3, the process is carried out in a hot water bath at a temperature of 65 ℃;
the recovery of oil phase (kerosene) was calculated to be 95%.
Example 8
The drugs used in this example were: 50ml of deionized water +0.5g of polyetheramine D400+0.784g of undecylenic acid +20ml of kerosene;
in the embodiment, kerosene is used for replacing oil-containing solid waste to establish a double-circulation extraction process;
step S1: mixing 50ml of deionized water and 0.5g of polyetheramine D400 to obtain a polyetheramine D400 aqueous solution;
step S2: placing white oil in a beaker, placing the beaker in a hot water bath at the temperature of 37 ℃, adding undecylenic acid in the beaker, and simultaneously and continuously performing magnetic stirring;
step S3: adding the polyetheramine D400 aqueous solution and continuously carrying out magnetic stirring is more favorable for leading the reaction system to react completely to achieve clear undecylenic acid ammonium salt solution and oil phase, wherein the upper layer is the oil phase, and the lower layer is the undecylenic acid ammonium salt solution;
step S4: separating to obtain a clear undecylenic acid ammonium salt solution and an upper layer liquid, wherein the upper layer liquid after standing comprises the following components: 19.6ml of a clear oil, 0.2ml of a white emulsion and 4.6ml of an ammonium undecylenate solution, wherein the white emulsion is an O/W emulsion (oil-in-water emulsion), by heating or by introducing CO2In the manner of (a) or (b),the demulsification of the white emulsion can be accelerated to obtain a separated oil phase and a separated water phase;
introducing CO into the clarified ammonium undecylenate solution2Protonating to obtain ammonium bicarbonate solution and lauric acid, separating to obtain ammonium bicarbonate solution, and returning undecylenic acid to step S2, wherein the process is carried out in a hot water bath at 37 deg.C;
step S5: introducing N into the ammonium bicarbonate solution2Deprotonation to obtain polyetheramine D400 aqueous solution and CO2，CO2Returning to step S4, the polyetheramine D400 aqueous solution returns to step S3, the process being carried out in a hot water bath at a temperature of 37 ℃;
the recovery of oil phase (kerosene) was calculated to be 98%.
As can be seen from examples 1 to 8 and test examples 1 and 2, organic acids were used as extractants and polyetheramines as CO which freed the organic acids from the oil phase2/N2The recovery rate of the oil obtained by recovering the switch type double-circulation extraction oil system is more than 90 percent.
The invention is not limited to the above alternative embodiments, and any other various forms of products can be obtained by anyone in the light of the present invention, but any changes in shape or structure thereof, which fall within the scope of the present invention as defined in the claims, fall within the scope of the present invention.
Claims (10)
1. CO (carbon monoxide)2/N2The switch type double-circulation extraction process is characterized in that oil-containing solid waste and organic acid are mixed and separated to obtain mixed liquor A and solid waste; adding the polyether amine aqueous solution into the mixed solution A to separate to obtain an oil phase and a mixed solution B, and introducing CO into the mixed solution B2Separating after protonation to obtain organic acid and mixed liquor C, returning the organic acid into the oil-containing solid waste, introducing N into the mixed liquor C2Deprotonation to give CO2And the aqueous solution of the polyether amine returns to the mixed solution A, CO2Returning to the mixed solution B, and controlling the temperature of the whole extraction process within the range of 30-70 ℃.
2. CO according to claim 12/N2The switch type double-circulation extraction process is characterized in that the organic acid is one or a mixture of more of fatty acids with 10-14 carbon atoms;
or one or more mixtures of C8-16 olefine acids.
3. CO according to claim 1 or 22/N2The switch type double-circulation extraction process is characterized in that the polyetheramine is polyetheramine D230 or polyetheramine D400.
4. CO according to claim 12/N2The switch type double-circulation extraction process is characterized in that the organic acid is n-decanoic acid, the polyether amine is polyether amine D230, and the temperature control range of the whole extraction process is 30-38 ℃.
5. CO according to claim 12/N2The switch type double-circulation extraction process is characterized in that the organic acid is lauric acid, the polyether amine is polyether amine D230, and the temperature control range of the whole extraction process is 55-67 ℃.
6. CO according to claim 12/N2The switch type double-circulation extraction process is characterized in that the organic acid is myristic acid, the polyether amine is polyether amine D230, and the temperature control range of the whole extraction process is 63-70 ℃.
7. CO according to claim 12/N2The switch type double-circulation extraction process is characterized in that the organic acid is undecylenic acid, the polyether amine is polyether amine D230, and the temperature control range of the whole extraction process is 33-37 ℃.
8. CO according to claim 12/N2The switch type double-circulation extraction process is characterized in that the polyether amine in the polyether amine aqueous solutionThe concentration is 0.5 to 23 weight percent, and the molar weight of the organic acid is 2 times of that of the polyether amine.
9. A CO according to any one of claims 1 to 82/N2The application of the switch type double-circulation extraction process in cleaning oil-containing solid waste.
10. The use according to claim 9, wherein the oil-containing solid waste is a refinery sludge.
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