CN109306852B - Reversible conversion degreasing agent containing tetrahydropyrane ring and preparation method and application thereof - Google Patents
Reversible conversion degreasing agent containing tetrahydropyrane ring and preparation method and application thereof Download PDFInfo
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- CN109306852B CN109306852B CN201710628815.8A CN201710628815A CN109306852B CN 109306852 B CN109306852 B CN 109306852B CN 201710628815 A CN201710628815 A CN 201710628815A CN 109306852 B CN109306852 B CN 109306852B
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 47
- 230000002441 reversible effect Effects 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000013527 degreasing agent Substances 0.000 title claims description 14
- 238000005237 degreasing agent Methods 0.000 title claims description 3
- 125000001412 tetrahydropyranyl group Chemical group 0.000 title abstract description 3
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 74
- 238000005553 drilling Methods 0.000 claims abstract description 74
- 238000000034 method Methods 0.000 claims abstract description 49
- 239000002699 waste material Substances 0.000 claims abstract description 49
- 239000002253 acid Substances 0.000 claims abstract description 17
- 239000003513 alkali Substances 0.000 claims abstract description 7
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical group C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 claims description 45
- 238000005520 cutting process Methods 0.000 claims description 38
- 239000012530 fluid Substances 0.000 claims description 37
- 239000007788 liquid Substances 0.000 claims description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- ODUCDPQEXGNKDN-UHFFFAOYSA-N nitroxyl Chemical compound O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- 150000001412 amines Chemical class 0.000 claims description 10
- 239000002585 base Substances 0.000 claims description 10
- 230000009467 reduction Effects 0.000 claims description 10
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 claims description 9
- 238000005984 hydrogenation reaction Methods 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910052790 beryllium Inorganic materials 0.000 claims description 5
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000006482 condensation reaction Methods 0.000 claims description 5
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 4
- 239000000920 calcium hydroxide Substances 0.000 claims description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 230000001351 cycling effect Effects 0.000 claims 1
- 238000000605 extraction Methods 0.000 abstract description 16
- 230000002209 hydrophobic effect Effects 0.000 abstract description 7
- 239000003921 oil Substances 0.000 description 168
- 238000011084 recovery Methods 0.000 description 17
- 238000009835 boiling Methods 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000010779 crude oil Substances 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000007429 general method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052699 polonium Inorganic materials 0.000 description 2
- HZEBHPIOVYHPMT-UHFFFAOYSA-N polonium atom Chemical compound [Po] HZEBHPIOVYHPMT-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B21/00—Methods or apparatus for flushing boreholes, e.g. by use of exhaust air from motor
- E21B21/06—Arrangements for treating drilling fluids outside the borehole
- E21B21/068—Arrangements for treating drilling fluids outside the borehole using chemical treatment
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- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Mining & Mineral Resources (AREA)
- Fluid Mechanics (AREA)
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Extraction Or Liquid Replacement (AREA)
Abstract
The invention provides a reversible oil removal agent containing a tetrahydropyrane ring, a preparation method and application thereof. The oil remover shown in the formula (I) shows hydrophobicity in a normal state, is converted into hydrophilicity after adding acid, and can be converted into hydrophobicity after adding alkali. The oil-based drilling waste oil removing treatment method has the advantages that the oil-based drilling waste oil removing treatment is realized by utilizing the hydrophilic and oleophilic convertibility of the oil-based drilling waste oil removing treatment method, specifically, the oil-based drilling waste oil is mixed with a hydrophobic oil removing conversion agent, the oil can be extracted into an oil removing agent, the oil removing agent is converted into hydrophilicity, the oil content obtained by extraction can be separated, and the oil removing agent is converted back into hydrophobicity to be continuously used for next oil removing treatment.
Description
Technical Field
The invention relates to an oil removing agent and a preparation method and application thereof, in particular to a reversible conversion oil removing agent containing a tetrahydropyran ring and a preparation method and application thereof, and belongs to the field of oil-based drilling waste treatment.
Background
Along with the development of unconventional oil and gas resources such as shale gas, the use scale of the oil-based drilling fluid is gradually increased. The oil-based drilling fluid takes diesel oil or industrial white oil as a continuous phase, and is added with emulsifying agents, wetting agents, filtrate loss reducers and other agents, so that the oil-based drilling fluid has good rheological property, fluid loss control property and lubricity.
In the drilling process, the solid control circulation system can generate a large amount of oil-based drilling cuttings, and the content of mineral oil in the oil-based drilling cuttings can reach 20%. After the drilling operation is finished, or the oil content in the waste oil-based drilling fluid after multiple cycles is up to more than 40%. In oil-based drilling cuttings and waste oil-based drilling fluids, except high content of mineral oil, the properties of the drilling fluids are stable and difficult to treat due to the action of agents such as emulsifiers, and the agents are listed in national hazardous waste records. Meanwhile, the high oil content has great resource recovery value. And the external unit is directly entrusted to process, thus wasting resources.
At present, the treatment methods of domestic and foreign oil-based drilling wastes (including oil-based drilling cuttings and waste oil-based drilling fluid) mainly comprise landfill, solidification, a solid-liquid separation method, an extraction method, a heat treatment method and the like. The landfill and solidification method relies on solid-liquid separation, extraction and heat treatment methods, and mainly landfills or solidifies the residue after separation by these methods. The heat treatment method recovery is to directly recover waste oil by adopting a heat treatment method such as distillation, and the recovered oil is influenced by the heat, and if the oil is used for further preparing the oil-based drilling fluid, the quality of the oil-based drilling fluid is influenced. The extraction method is to extract the waste oil by using an extractant, and then recover the extractant by means of heating or pressurizing and the like, and compared with the recovery by a heat treatment method, the extraction method does not damage oil products, so the extraction method is commonly used, but the prior extractant has the following technical problems:
(1) the addition of the extracting agent is large, the extraction rate is low, the recovery is difficult, and the cost is high;
(2) the recovery of the extractant needs complex means such as heating or pressurizing, needs larger equipment investment, and is not beneficial to industrial application;
(3) the adaptability of the extracting agent is not strong;
(4) the boiling point of the extractant is low (30-40 ℃), and the use safety is low.
In view of the above, there is a need in the art to develop a new oil-based drilling waste treatment agent and a new treatment method to meet the needs of the existing oil-based drilling waste treatment agent and treatment method.
Disclosure of Invention
In view of the actual needs, the main object of the present invention is to provide a reversible conversion oil remover containing tetrahydropyran ring, which can be applied to the field of oil-based drilling waste treatment, and which can effectively overcome one or more of the defects of the existing extractants.
Another object of the present invention is to provide a method for preparing the above reversible conversion oil-removing agent containing a tetrahydropyran ring, by which the oil-removing agent can be efficiently prepared.
The invention further aims to provide application of the reversible conversion oil removal agent containing the tetrahydropyran ring.
In order to achieve the above object, the present invention provides a reversible conversion degreaser containing a tetrahydropyran ring, which has a structural formula shown in formula (I):
wherein R in the formula (I)1、R2Each independently selected from methyl or ethyl.
Preferably, formula (I) is selected from:
the oil remover shown in the formula (I) shows hydrophobicity in a normal state, is converted into hydrophilicity after adding acid, and can be converted into hydrophobicity after adding alkali. The oil-based drilling waste oil removing treatment method is characterized in that the oil-based drilling waste oil removing treatment is realized by utilizing the hydrophilic and oleophilic convertibility of the oil-based drilling waste oil removing treatment method, specifically, the oil-based drilling waste oil is mixed with a hydrophobic oil removing conversion agent, oil can be extracted into an oil removing agent, the oil removing agent is converted into hydrophilicity, oil obtained by extraction can be separated, and the oil removing agent is converted back to hydrophobicity to be continuously used for next oil removing treatment. The oil removing agent for treating oil-based drilling waste has high oil removing rate, the oil recovery rate is over 95 percent, the oil content of residual waste water after oil removal is less than 5mg/L, and the oil content of residual solid residues is less than 0.3 percent. The oil removal agent has broad spectrum and can be widely used for treating oil-containing drilling wastes such as different oil-based drilling waste liquids, drilling cuttings and the like in petroleum and petrochemical enterprises. In addition, the oil removing agent has the advantages of good recovery rate, reusability, high boiling point of about 78 ℃, good use safety and the like.
On the other hand, the invention provides a preparation method of the reversible conversion degreaser containing the tetrahydropyran ring, which comprises the steps of firstly carrying out condensation reaction on tetrahydropyranone shown in a formula (A) and organic amine to form ketoamine shown in a formula (B), then carrying out hydrogenation reduction on the ketoamine, and then separating out upper liquid to obtain the reversible conversion degreaser containing the tetrahydropyran ring;
specifically, the scheme is carried out according to the following route:
in the above preparation method, preferably, the organic amine includes one or more of dimethylamine, diethylamine and methylethylamine.
In the above preparation method, preferably, the hydrogenation reduction of the ketoamine is reduction of the ketoamine by passing hydrogen gas in the presence of a metal catalyst. More preferably, the metal catalyst comprises one or more of beryllium, rhodium, nickel and palladium. Further preferably, the mass ratio of the metal catalyst to the ketoamine is 1-100: 1 to 800. More preferably, the hydrogenation reduction of the ketoamine is carried out for 2-8 h under the conditions that the hydrogen pressure is 20-40 MPa and the temperature is 50-140 ℃. For example, the reaction is carried out under the conditions of 20 to 25MPa and the temperature of 50 to 70 ℃ for 2 to 4.
In the preparation method, preferably, the volume ratio of the tetrahydropyranone to the organic amine is 120-150: 200 to 300. More preferably, the condensation reaction is carried out at 50-140 ℃ for 2-8 h.
As a specific example of the above preparation method, it comprises the following steps:
(1) taking 1 500mL of three-neck flask, putting into a heating jacket, weighing 120-150 mL of tetrahydropyranone at room temperature, adding into the flask, and starting stirring;
(2) meanwhile, adding 200-300 mL of organic amine, continuously stirring, and fully dissolving;
(3) reacting for 7-10 h;
(4) the solution after the reaction is transferred into a 1000mL reaction kettle, and H is introduced2Adding 0.2g of metal catalyst, and reacting for 2-4 h under the conditions of 20-25 MPa pressure and 50-70 ℃;
(5) the separated upper layer liquid is the target product reversible conversion degreaser containing tetrahydropyran ring;
the organic amine is selected from 1 or 2 of dimethylamine, diethylamine and methylethylamine;
the metal catalyst is selected from 1 or 2 of beryllium, polonium and palladium.
In another aspect, the invention provides the use of the reversible conversion degreaser containing a tetrahydropyran ring as an extractant for recovering oil from oil-based drill cuttings.
In another aspect, the present invention provides a method of treating oil-based drill cuttings, comprising the steps of:
(1) fully mixing the reversible conversion oil removal agent containing the tetrahydropyran ring with the oil-based drilling cuttings, and adding water;
(2) adding acid into the liquid obtained in the step (1);
(3) standing the liquid obtained in the step (2), and separating and recovering oil on the upper layer;
(4) and (4) adding alkali into the residual liquid after the oil is extracted in the step (3), standing, layering and separating to obtain the reversible conversion oil removal agent containing the tetrahydropyran ring.
Preferably, the step (4) is followed by repeating the steps (1) to (3) with the reversible conversion degreaser containing a tetrahydropyran ring obtained therefrom.
Preferably, the oil content of the oil-based drilling cuttings is 5-30%.
In the step (1) of the method for treating oil-based drill cuttings, the mass ratio of the reversible conversion oil removal agent containing a tetrahydropyran ring to the oil-based drill cuttings and water is preferably 2: 1-4: 1.
in the above method for treating oil-based drill cuttings, preferably, the molar ratio of the acid in step (2) to the tetrahydropyran ring-containing reversible oil-removing agent in step (1) is 1: 5-2: 1. more preferably, the acid comprises one or more of hydrogen chloride, sulfuric acid, phosphoric acid. Further preferably, the acid is added in the form of an aqueous solution. For example, hydrochloric acid with a mass fraction of 36%.
In the above method for treating oil-based drill cuttings, preferably, the molar ratio of the base in step (4) to the tetrahydropyran ring-containing reversible conversion degreaser in step (1) is 1: 2-3: 1. more preferably, the base comprises one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide. Further preferably, the base is added in the form of an aqueous solution. For example, 10% by mass sodium hydroxide.
In another aspect, the invention provides the use of the reversible conversion oil removal agent containing a tetrahydropyran ring as an extractant for recovering oil in an oil-based drilling fluid.
In another aspect, the present invention provides a method of treating a waste oil-based drilling fluid comprising the steps of:
(1) fully mixing the reversible conversion oil removal agent containing the tetrahydropyran ring with the waste oil-based drilling fluid, and adding water;
(2) adding acid into the liquid obtained in the step (1);
(3) standing the liquid obtained in the step (2), and separating and recovering oil on the upper layer;
(4) and (4) adding alkali into the residual liquid after the oil is extracted in the step (3), standing, layering and separating to obtain the reversible conversion oil removal agent containing the tetrahydropyran ring.
Preferably, the step (4) is followed by repeating the steps (1) to (3) with the reversible conversion degreaser containing a tetrahydropyran ring obtained therefrom.
In the step (1) of the method for treating the waste oil-based drilling fluid, the oil content of the waste oil-based drilling fluid is preferably 20-75%.
In the step (1) of the method for treating the waste oil-based drilling fluid, the mass ratio of the reversible conversion oil removal agent containing a tetrahydropyran ring to the waste oil-based drilling fluid and water is preferably 1: 1-3: 1.
in the above method for treating a waste oil-based drilling fluid, preferably, the molar ratio of the acid in step (2) to the reversible conversion degreaser containing a tetrahydropyran ring in step (1) is 1: 5-2: 1. more preferably, the acid comprises one or more of hydrogen chloride, sulfuric acid, phosphoric acid. Further preferably, the acid is added in the form of an aqueous solution. For example, hydrochloric acid with a mass fraction of 36%.
In the above method for treating a waste oil-based drilling fluid, preferably, the molar ratio of the base in step (4) to the reversible conversion degreaser containing a tetrahydropyran ring in step (1) is 1: 2-3: 1. more preferably, the base comprises one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide. Further preferably, the base is added in the form of an aqueous solution. For example, 10% by mass sodium hydroxide.
In summary, the invention mainly provides a reversible conversion oil removal agent containing tetrahydropyran ring, a preparation method and an application thereof, and the reversible conversion oil removal agent has the following advantages:
(1) the oil removing effect is good. After oil removal and extraction treatment, the oil content of oil-based drilling cuttings with the oil content of more than 20 percent is less than 0.3 percent, and the oil content of crude oil is more than 97 percent.
(2) Can be repeatedly used, the recovery mode is simple, and the recovery rate is high. By adding acid or alkali, the oil removing agent can be continuously switched in a hydrophilic-hydrophobic state, so that the oil removing agent is convenient to recycle, and the recovery rate is over 95 percent. Compared with the heating and pressurizing recovery mode adopted by the prior extracting agent, the method is safer and is easier to operate.
(3) Has strong broad spectrum. The oil removing agent has good adaptability, and can be widely used for removing oil from oil-containing drilling wastes such as drilling waste liquid, drilling cuttings and the like with different oil field blocks and different oil contents.
(4) High boiling point and high safety. The defects of low boiling point (30-40 ℃), flammable and explosive risks and the like of a common extracting agent are overcome, and the safety and the use conditions of the oil removing agent are improved.
Detailed Description
For a more clear understanding of the technical features, objects and advantages of the present invention, reference is now made to the following detailed description taken in conjunction with the accompanying specific embodiments, and the technical solutions of the present invention are described, it being understood that these examples are intended to illustrate the present invention and are not intended to limit the scope of the present invention. In the examples, each raw reagent material is commercially available, and the experimental method not specifying the specific conditions is a conventional method and a conventional condition well known in the art, or a condition recommended by an instrument manufacturer.
The room temperature of the invention is 18-30 ℃.
Example 1
The present embodiment provides an oil removal agent represented by formula (I-1) and a preparation method thereof, the preparation method including the steps of:
(1) taking 1 500mL of three-neck flask, putting into a heating sleeve, weighing 120mL of tetrahydropyranone (CAS number: 29943-42-8) at room temperature, adding into the flask, and stirring;
(2) simultaneously adding 200mL of dimethylamine, continuously stirring and fully dissolving;
(3) reacting for 7 h;
(4) the solution after the reaction is transferred into a 1000mL reaction kettle, and H is introduced2Adding 0.2g of metal catalyst beryllium, and reacting for 2 hours under the conditions of 20MPa pressure and 50 ℃;
(5) the separated upper layer liquid is the target product of the reversible conversion oil removal agent containing the tetrahydropyran ring shown in formula (I-1), the boiling point of the reversible conversion oil removal agent is tested according to GB/T616-2006 general method for measuring the boiling point of chemical reagents, and the obtained results are shown in Table 1.
Example 2
The present embodiment provides an oil removal agent represented by formula (I-2) and a preparation method thereof, the preparation method including the steps of:
(1) taking 1 500mL of three-neck flask, putting into a heating sleeve, weighing 135mL of tetrahydropyranone (CAS number: 29943-42-8) at room temperature, adding into the flask, and stirring;
(2) meanwhile, 260mL of diethylamine is added, and stirring is continued to fully dissolve;
(3) reacting for 8.5 h;
(4) the solution after the reaction is transferred into a 1000mL reaction kettle, and H is introduced2Adding 0.2g of polonium as a metal catalyst, and reacting for 3 hours under the conditions of 22MPa pressure and 60 ℃;
(5) the separated upper layer liquid is the target product of the reversible conversion oil removal agent containing the tetrahydropyran ring shown in formula (I-2), the boiling point of the reversible conversion oil removal agent is tested according to GB/T616-2006 general method for measuring the boiling point of chemical reagents, and the obtained results are shown in Table 1.
Example 3
The present embodiment provides an oil removal agent represented by formula (I-3) and a preparation method thereof, the preparation method including the steps of:
(1) taking 1 500mL of three-neck flask, putting into a heating sleeve, weighing 150mL of tetrahydropyranone (CAS number: 29943-42-8) at room temperature, adding into the flask, and stirring;
(2) simultaneously adding 300mL of ethylamine, continuously stirring and fully dissolving;
(3) reacting for 10 h;
(4) the solution after the reaction is transferred into a 1000mL reaction kettle, and H is introduced2Adding 0.2g of metal catalyst palladium, and reacting for 4 hours under the conditions of 25MPa pressure and 70 ℃;
(5) the separated upper layer liquid is the reversible conversion oil removal agent containing the tetrahydropyran ring shown in the target product (I-3), the boiling point of the reversible conversion oil removal agent is tested according to GB/T616-2006 general method for measuring the boiling point of chemical reagents, and the obtained results are shown in Table 1.
Evaluation of the oil-removing agent obtained in examples
(1) Method for evaluating oil removal effect of reversible conversion oil removal agent on oil-based drilling cuttings
(1.1) fully mixing 20mL of reversible oil removal agent and 40.0g of oil-based drilling cuttings, fully shaking, and adding 20mL of pure water;
(1.2) dropwise adding 5ml of HCl solution (36%) into the liquid in the step (1.1) while stirring until the bottom of the mixed liquid is clear and large oil droplets appear; at the moment, the oil removing agent is changed from hydrophobic to hydrophilic;
(1.3) standing the liquid obtained in (1.2) for 15 minutes, and separating and recovering the upper oil layer;
(1.4) adding 5ml of aqueous solution of NaOH (40%) into the residual liquid (1.2) after oil extraction while stirring until the liquid is layered, and then the oil removing agent becomes hydrophobic again, so that oil removal extraction treatment can be carried out on new oil-based drilling cuttings again.
(2) Method for evaluating oil removal effect of reversible conversion oil removal agent on waste oil-based drilling fluid
(2.1) fully mixing 20mL of reversible oil removal agent and 20.0g of waste oil-based drilling fluid, fully shaking, and adding 20mL of pure water;
(2.2) dropwise adding 5mL of HCl solution (36%) into the liquid in the step (2.1) while stirring until the bottom of the mixed liquid is clear and large oil drops appear; at the moment, the oil removing agent is changed from hydrophobic to hydrophilic;
(2.3) standing the liquid obtained in the step (2.2) for 15 minutes, and separating and recovering oil on the upper layer;
(2.4) adding 5mL of NaOH aqueous solution (40%) into the residual liquid (2.2) after oil extraction while stirring until the liquid is layered, and then the oil removal agent becomes hydrophobic again, so that oil removal extraction treatment can be carried out on new waste oil-based drilling fluid again.
(3) Oil removal rate calculation method
(3.1) calculating the oil content of the crude oil extraction by the following formula:
oil content (mass percent)
Wherein W is sample mass, g;
Vw-distilled water volume, mL;
ρwdensity of water, g/mL.
Wf-mass of filter residue, g.
(3.2)
In the formula Woe-crude oil extraction quality, g;
Poe-crude oil content (mass percent);
Wom-oil based drill cuttings quality, g;
Pomoil content (mass percent) of oil-based drill cuttings;
(3.3) method for detecting oil content of residue
Determination of oil content of residue after oil removal of oil-based drilling cuttings and waste oil-based drilling fluid by using CJ/T221-
(3.4) reversible conversion degreaser recovery rate detection method
The water content of the hydrophobic liquid recovered after the reversible conversion process was measured using the GB 260-77 petroleum product moisture assay.
(3.5) evaluation results of the products of examples
The oil-based drilling cuttings with the oil content of 20.25% in a certain shale gas area block are selected as research objects, and the evaluation results of the products in the embodiment are shown in table 1.
Table 1 oil removal and recovery evaluation of the products of the examples on oil-based drill cuttings
The waste oil-based drilling fluid with the oil content of 64.3% in a certain shale gas block is selected as a research object, and the evaluation results of the products in the embodiment are shown in table 2.
TABLE 2 oil removal and recovery evaluation of the products of the examples on waste oil based drilling fluids
As can be seen from tables 1 and 2, the boiling points of the oil removal agents obtained in the 3 examples of the present invention are all about 78 ℃, and the boiling points are significantly higher than those of the conventional extraction agents. When the oil removing agent is used for treating oil-based drilling cuttings and waste oil-based drilling fluid, the crude oil content is more than 97%, the oil removing rate is more than 97%, and as a result of treating the drilling cuttings, the oil content of residues is less than 0.3%, and the recovery rate of the oil removing agent is more than 95%, so that the oil removing agent has the advantages of good recovery rate of oil in the recovered oil-based drilling cuttings and good recovery rate of the oil removing agent.
Finally, the description is as follows: although the present invention has been described in detail with reference to the above embodiments, it should be understood by those skilled in the art that: modifications and equivalents may be made thereto without departing from the spirit and scope of the invention and it is intended to cover any modifications or equivalents as may fall within the scope of the invention.
Claims (23)
1. An oil remover containing a tetrahydropyran ring, which has a structural formula shown in formula (I):
wherein R in the formula (I)1、R2Each independently selected methyl or ethyl;
the oil remover is prepared by the following preparation method:
firstly, carrying out condensation reaction on tetrahydropyranone shown in a formula (A) and organic amine to form ketoamine shown in a formula (B), then carrying out hydrogenation reduction on the ketoamine, and then separating out upper-layer liquid to obtain the degreasing agent containing tetrahydropyran rings;
the organic amine comprises one or more of dimethylamine, diethylamine and methylethylamine;
the step of hydrogenation reduction of the ketoamine is to introduce hydrogen to reduce the ketoamine in the presence of a metal catalyst; the metal catalyst comprises one or more of beryllium, rhodium, nickel and palladium; the mass ratio of the metal catalyst to the ketoamine is 1-100: 1-800; the ketoamine is subjected to hydrogenation reduction for 2-8 h under the conditions that the hydrogen pressure is 20-40 MPa and the temperature is 50-140 ℃.
2. The oil remover containing a tetrahydropyran ring according to claim 1, wherein formula (I) is selected from:
3. the method for preparing the oil remover containing the tetrahydropyran ring according to claim 1 or 2, which comprises the steps of firstly carrying out condensation reaction on tetrahydropyranone shown in a formula (A) and organic amine to form ketoamine shown in a formula (B), then carrying out hydrogenation reduction on the ketoamine, and then separating out upper liquid to obtain the oil remover containing the tetrahydropyran ring;
the organic amine comprises one or more of dimethylamine, diethylamine and methylethylamine;
the step of hydrogenation reduction of the ketoamine is to introduce hydrogen to reduce the ketoamine in the presence of a metal catalyst;
the metal catalyst comprises one or more of beryllium, rhodium, nickel and palladium;
the mass ratio of the metal catalyst to the ketoamine is 1-100: 1-800;
the ketoamine is subjected to hydrogenation reduction for 2-8 h under the conditions that the hydrogen pressure is 20-40 MPa and the temperature is 50-140 ℃.
4. The preparation method according to claim 3, wherein the volume ratio of the tetrahydropyranone to the organic amine is 120-150: 200 to 300.
5. The method according to claim 3, wherein the condensation reaction is carried out at 50 to 140 ℃ for 2 to 8 hours.
6. Use of the tetrahydropyran ring-containing oil remover according to claim 1 or 2 as an extractant for recovering oil from oil-based drill cuttings.
7. A method of treating oil-based drill cuttings, comprising the steps of:
(1) thoroughly mixing the oil remover containing a tetrahydropyran ring according to claim 1 or 2 with the oil-based drill cuttings, and adding water;
(2) adding acid into the liquid obtained in the step (1);
(3) standing the liquid obtained in the step (2), and separating and recovering oil on the upper layer;
(4) and (4) adding alkali into the residual liquid after the oil is extracted in the step (3), standing, layering and separating to obtain the oil removing agent containing the tetrahydropyran ring.
8. The method for treating oil-based drill cuttings according to claim 7, wherein the step (4) is followed by repeatedly cycling the step (1) to the step (3) with the tetrahydropyran ring-containing oil removal agent obtained therefrom.
9. The method of treating oil-based drill cuttings according to claim 7, wherein the oil content of the oil-based drill cuttings is between 5 and 30%.
10. The method for treating oil-based drill cuttings according to any one of claims 7 to 9, wherein the mass ratio of the tetrahydropyran ring-containing oil remover to the oil-based drill cuttings and water in step (1) is 2: 1-4: 1.
11. the method for treating oil-based drill cuttings according to any one of claims 7 to 9, wherein the molar ratio of the acid in step (2) to the tetrahydropyran ring-containing oil remover in step (1) is 1: 5-2: 1.
12. the method of treating oil-based drill cuttings according to claim 11, wherein the acid comprises one or more of hydrogen chloride, sulfuric acid, and phosphoric acid.
13. The method for treating oil-based drill cuttings according to any one of claims 7 to 9, wherein the molar ratio of the base in step (4) to the tetrahydropyran ring-containing oil removal agent in step (1) is 1: 2-3: 1.
14. the method of treating oil-based drill cuttings according to claim 13, wherein the base comprises one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide.
15. Use of the tetrahydropyran ring containing oil-removing agent of claim 1 or 2 as an extractant for recovering oil in an oil-based drilling fluid.
16. A method of treating a waste oil-based drilling fluid comprising the steps of:
(1) thoroughly mixing the oil removing agent containing a tetrahydropyran ring according to claim 1 or 2 with the waste oil-based drilling fluid, and adding water;
(2) adding acid into the liquid obtained in the step (1);
(3) standing the liquid obtained in the step (2), and separating and recovering oil on the upper layer;
(4) and (4) adding alkali into the residual liquid after the oil is extracted in the step (3), standing, layering and separating to obtain the reversible conversion oil removal agent containing the tetrahydropyran ring.
17. A method of treating a waste oil-based drilling fluid according to claim 16, wherein the step (4) is followed by repeated cycles of steps (1) to (3) with the tetrahydropyran ring containing oil removal agent obtained therefrom.
18. The method of treating a waste oil-based drilling fluid of claim 16, wherein the oil content of the waste oil-based drilling fluid is 20-75%.
19. The method for treating the waste oil-based drilling fluid according to any one of claims 16 to 18, wherein the mass ratio of the oil removing agent containing the tetrahydropyran ring to the waste oil-based drilling fluid and water is 1: 1-3: 1.
20. the method for treating the waste oil-based drilling fluid according to any one of claims 16 to 18, wherein the molar ratio of the acid in the step (2) to the oil removing agent containing the tetrahydropyran ring in the step (1) is 1: 5-2: 1.
21. the method of treating a waste oil-based drilling fluid of claim 20, wherein the acid comprises one or more of hydrogen chloride, sulfuric acid, phosphoric acid.
22. A method of treating a waste oil-based drilling fluid according to claim 16 or 17, wherein the molar ratio of the base in step (4) to the tetrahydropyran ring containing oil removal agent in step (1) is 1: 2-3: 1.
23. the method of treating a waste oil-based drilling fluid of claim 22, wherein the base comprises one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide.
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