CN108003108B - Triazine natural gas drag reducer and preparation method and application thereof - Google Patents
Triazine natural gas drag reducer and preparation method and application thereof Download PDFInfo
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- CN108003108B CN108003108B CN201610967630.5A CN201610967630A CN108003108B CN 108003108 B CN108003108 B CN 108003108B CN 201610967630 A CN201610967630 A CN 201610967630A CN 108003108 B CN108003108 B CN 108003108B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/54—Three nitrogen atoms
- C07D251/70—Other substituted melamines
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/14—Nitrogen-containing compounds
- C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17D—PIPE-LINE SYSTEMS; PIPE-LINES
- F17D1/00—Pipe-line systems
- F17D1/02—Pipe-line systems for gases or vapours
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Abstract
The invention discloses a triazine natural gas drag reducer. The molecular structural formula is as follows:
. The drag reducer is synthesized by the following method: dissolving cyanuric chloride in a solvent, dropwise adding morpholine and inorganic base at-15-0 ℃, reacting for 4-12 h at 0-50 ℃, adding secondary amine and inorganic base after the reaction is finished, reacting for 6-15 h at 60-100 ℃, and washing with water after the reaction is finished to obtain the product. The drag reducer provided by the invention has a multi-polar end and a non-polar end, and has good adsorption performance and excellent drag reduction and delivery increase effects. The invention has the advantages of simple synthesis process, mild condition, short time, low requirement on equipment and easy realization of large-scale industrial production.
Description
Technical Field
The invention belongs to the field of organic chemistry, and particularly relates to a triazine natural gas drag reducer as well as a preparation method and application thereof.
Background
As an efficient and clean energy source, natural gas has become the best choice for improving the environment and promoting the sustainable development of economy in all countries of the world, and the demand of natural gas is increasing day by day.
At present, the main transportation mode of natural gas is pipeline transportation. However, in the process of transporting natural gas by a pipe, the roughness of the inner wall of the pipe can generate frictional resistance, so that gas vortex is generated, and the pressure drop along the way and the energy loss are caused. Therefore, to increase the gas transportation amount, it is necessary to reduce the resistance during the transportation of the natural gas and reduce the energy loss. At present, the main methods for reducing drag and increasing delivery are an inner coating drag reduction technology and a drag reducer drag reduction technology. The natural gas drag reducer can obviously increase the output, save energy, reduce consumption, meet the seasonal peak load regulation of in-service pipelines, improve the operation safety factors of full-load operation pipelines and corrosion aging pipelines, and the like. The natural gas drag reducer has great economic value and application potential, and has good actual production demand and market prospect.
The natural gas drag reducer is a compound similar to a surfactant structure, has a polar end and a non-polar end, after the natural gas drag reducer is filled into a pipeline, the polar end is adsorbed on the inner wall of the pipeline through a coordination bond, and the non-polar end exists between a fluid and the inner surface of the pipeline and is suspended in an airflow in a downstream direction under the action of shear stress to form a layer of film. The film can partially fill the depressions on the wall surface of the tube, and serves to reduce roughness. Meanwhile, in the process of recovering and extending the molecules, part of energy of the fluid molecules impacting the inner wall is absorbed and returned to the fluid, the radial pulsation of the gas and the pulsation generated by the rough bulges are reduced, and the vortex energy is reduced, so that the flow resistance is reduced, and the aim of reducing the resistance is fulfilled. Therefore, the development of natural gas drag reducers with strong polar-end adsorptivity and moderate flexible-end has become one of the active petrochemical additive fields in recent years.
US 5902784A and Chinese patent CN 101575495A respectively disclose a synthetic method of a nitrogen-containing natural gas drag reducer and are used for drag reduction and transportation enhancement of a gas pipeline, CN 102040908A discloses that trimethoxy silane and α -dodecene are used as raw materials, and under the condition of the presence of a platinum catalyst, the dodecyl trimethoxy silane drag reducer is synthesized, and the Mannich base drag reducer synthesized by a two-step method in patent CN 101328442A can be applied to drag reduction and transportation enhancement of a natural gas gathering and transportation pipeline.
In addition, there are some reports on the synthesis of nitrogen-containing drag reducers, such as patent CN 102838606 a also discloses the preparation of a porphyrin-based natural gas drag reducer, and patent CN 101575497 a; US 5549848A; CN 101328441A; CN 101329011A; w.g. Xing et al (polymer. degrad. stab. 2011, 92: 74-78); asahi et al (Natural gas industry 2010, 30: 92-96). Patents CN 102443022A and CN 102863473 a report phosphorous drag reducers octadecyl alcohol phosphate ammonium salts and six-membered cycloalkyl siloxane-phosphate esters, respectively.
However, the natural gas drag reducers reported in the above patents and documents have some disadvantages, mainly including single polar end, weak adsorptivity, few non-polar ends (such as octadecyl alcohol phosphate ammonium salt), unobvious drag reduction effect, and poor solubility (such as hexa-membered cyclic alkyl siloxane-phosphate), which cannot be applied to natural gas pipeline drag reduction in large scale, so the application range is greatly limited, and the drag reduction effect needs to be further improved.
Disclosure of Invention
Aiming at the defects of poor adsorptivity, few polar chain ends and poor drag reduction effect of the conventional natural gas drag reducer, the invention provides a triazine natural gas drag reducer and a synthesis method thereof. The drag reducer has the characteristics of strong multi-polar-end adsorption and good drag reduction effect. The synthesis method is simple, the reaction time is short, and the solvent is low in toxicity and pollution-free.
The invention provides a triazine drag reducer, which has a molecular structural formula shown as a formula (I):
in the formula (I), R is any one of cyclohexyl or phenyl.
The invention also provides a preparation method of the triazine drag reducer, which comprises the following steps:
dissolving cyanuric chloride in a solvent, adding morpholine and inorganic base at-15-0 ℃, reacting for 4-12 h at 0-50 ℃, and stopping the reaction; adding secondary amine and inorganic base under stirring, and reacting for 6-15 h at the temperature of 60-100 ℃; and after the reaction is finished, carrying out suction filtration, washing the crude product with water, and drying at the temperature of 60-150 ℃ for 6-12 h to obtain the triazine drag reducer.
In the present invention, the molar ratio of cyanuric chloride to morpholine is generally 1: 2-1: 3, preferably 1: 2-1: 2.5; the molar ratio of morpholine to inorganic base is generally 1: 2-1: 3, preferably 1: 2-1: 2.5; the molar ratio of cyanuric chloride to secondary amine is generally 1: 1-1: 2, preferably 1: 1-1: 1.5; the molar ratio of secondary amine to inorganic base is generally 1: 1-1: 2, preferably 1: 1-1: 1.5.
in the invention, the solvent is selected from one or more of acetone, toluene and water, and is preferably acetone.
In the invention, the secondary amine can be any one of dicyclohexylamine or diphenylamine.
In the present invention, the inorganic base is selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate, and is preferably sodium hydroxide.
The synthetic route of the triazine drag reducer is as follows:
the invention also provides application of the synthesized natural gas drag reducer in natural gas pipeline transportation. The drag reducer synthesized by the invention can improve the gas transmission amount, reduce the gas transmission power and meet the requirement of seasonal peak regulation in the natural gas pipeline transportation, and can reduce the danger of full-load operation to a certain extent. In addition, the synthesized drag reducer can also play an auxiliary role in inhibiting corrosion, repairing internal coating defects and the like.
The product of the invention is used as a natural gas drag reducer, and is generally prepared into solutions of ethanol, gasoline, diesel oil or acetone and the like to be applied to the drag reduction and transportation increase process of a natural gas pipeline. The content of the triazine natural gas drag reducer in the prepared solution is generally 5-200 g/L.
The triazine natural gas drag reducer provided by the invention is a compound with a multi-polar end and a non-polar end. As a drag reduction additive of a natural gas pipeline, after the drag reduction additive is atomized and injected or coated on the inner wall of the pipeline, the polar end of the drag reduction additive is firmly adsorbed on the inner surface of the metal of the pipeline and forms a smooth film, while the non-polar end exists between the fluid of the pipeline and the inner surface, part of the drag reduction additive fills the dent of the inner surface of the pipeline to reduce the roughness, the non-polar end is suspended in the airflow downstream under the action of shear stress, the energy of part of the fluid molecules impacting the inner wall is absorbed and returned to the fluid in the process of recovering and extending the molecules, the radial pulsation of the gas and the pulsation generated by the rough bulge are. The product of the invention is white or light yellow solid, the yield is more than 85 percent, and the product has good adsorption performance and excellent drag reduction and delivery increase effects on the metal surface.
The drag reducer has the advantages of simple synthesis process, mild reaction conditions, short reaction time, low equipment requirement and easy realization of large-scale industrial production, and overcomes the defects of poor adsorptivity and short drag reduction effect duration of the conventional natural gas drag reducer.
Drawings
FIG. 1 is a graph showing electrochemical impedance spectra of a white iron electrode and the iron electrode after film formation using the drag reducer obtained in example 1.
Detailed Description
The triazine based natural gas drag reducing agent and the method for preparing the same of the present invention are further illustrated by the following examples, which are provided only for illustrating the present invention and are not intended to limit the present invention.
In the examples, electrochemical tests and data analysis were carried out on the samples tested using an electrochemical workstation, IM6, ZAHZER, germany; the used indoor loop test evaluation device is a self-made test device.
Example 1
110.4g of cyanuric chloride and 600mL of acetone were placed in a 3000mL four-necked flask equipped with a reflux condenser, a thermometer, a stirrer and a constant pressure dropping funnel, the four-necked flask was cooled to-15 ℃ and 104.4g of morpholine and 480.0g of 10wt.% sodium hydroxide solution were slowly dropped while stirring, and the temperature of the system was controlled to not exceed 0 ℃. After dropping, the system is slowly heated to 40 ℃ to react for 8 h. The reaction was stopped, and 60.7g of dicyclohexylamine and 240.0g of 10w.t.% sodium hydroxide solution were added to the system, and reacted at 90 ℃ for 10 hours. After the reaction, the reaction solution was filtered, and the crude product was washed with distilled water and dried at 100 ℃ to obtain 231.2g of a white product with a yield of 89.6%.
The structural formula of the product obtained in this example is as follows:
and (4) performing electrochemical test. The iron electrode (Q235) was encapsulated with epoxy, exposing only the tip to contact the solution. Before each experiment, the surface of the iron electrode is polished to a mirror surface by using No. 2000 abrasive paper, washed by water and ethanol, naturally dried, sprayed with 20g/L of prepared drag reducer ethanol solution, and naturally dried. A three-chamber electrolytic cell is adopted, a working electrode is an iron electrode, a reference electrode is a saturated calomel electrode, a platinum electrode is an auxiliary electrode, a sine perturbation signal with the amplitude of 5mV is selected, the sine perturbation signal is scanned from high frequency to low frequency within the frequency range of 0.02Hz-60kHz, and electrochemical impedance spectroscopy test is carried out in 3.5% NaCl solution. The film forming property of the drag reducer on the surface of the steel is tested by electrochemical impedance spectroscopy.
FIG. 1 is the electrochemical impedance spectrum of a blank iron electrode and the iron electrode after film formation. The literature reports that the charge transfer resistance of the film is increased, and the capacitive arc is also increased, so that the higher the low-frequency arc is, the better the barrier effect of the film on the surface electrode process and the film forming effect on the iron electrode are. Because the iron electrode is in a semicircular capacitive arc resistance in a low-frequency area, the electrochemical reaction process of the surface of the iron electrode is mainly controlled by a charge transfer process. As can be seen from fig. 1, the blank sample has a smaller capacitive arc resistance, indicating that the blocking effect of the iron electrode without film formation is smaller. After the film of the drag reducer is formed on the surface of the iron electrode, two continuous capacitive arcs are formed from a high frequency area to a low frequency area. The smaller capacitive arc is formed in a high-frequency area and is the capacitive arc of film formation of the drag reducer, which shows that the drag reducer forms a barrier film on the surface of an iron electrode, and then forms a larger capacitive arc in a low-frequency area, and is the capacitive arc of the iron electrode after film formation, and the diameter of the capacitive arc is larger than that of a blank iron electrode.
Indoor loop test analysis shows that the product is prepared into ethanol solution, atomized and injected into a loop, the test pressure is 0.5-0.6MPa, when the concentration of the drag reducer is 50g/L, the average drag reduction rate can reach 8.3%, and the effective period is more than 60 days.
Example 2
110.4g of cyanuric chloride and 600mL of acetone were placed in a 3000mL four-necked flask equipped with a reflux condenser, a thermometer, a stirrer and a constant pressure dropping funnel, the four-necked flask was cooled to-15 ℃ and 104.4g of morpholine and 480.0g of 10w.t.% sodium hydroxide solution were slowly dropped while stirring, and the temperature of the system was controlled to not exceed 0 ℃. After dropping, the system is slowly heated to 50 ℃ to react for 8 h. The reaction was stopped, and 60.7g of diphenylamine and 240.0g of 10w.t.% sodium hydroxide solution were added to the system, and reacted at 100 ℃ for 10 hours. After the reaction, the reaction mixture was filtered, and the crude product was washed with distilled water and dried at 100 ℃ to obtain 219.3g of a pale yellow product with a yield of 87.5%.
The structural formula of the product obtained in this example is as follows:
indoor loop test analysis shows that the product is prepared into ethanol solution, atomized and injected into a loop, the test pressure is 0.5-0.6MPa, when the concentration of the drag reducer is 40g/L, the average drag reduction rate can reach 8.0%, and the effective period is more than 60 days.
Example 3
The solvent used in this example was 500mL of toluene in step one, otherwise the same as in example 1. 223.7g of a white product was obtained in 86.7% yield.
Example 4
This example used 100.8g of inorganic base and 50.4g of sodium bicarbonate in step one, the rest being the same as example 1. 221.6g of white product was obtained in 85.9% yield.
Claims (3)
1. The application of the triazine compound in natural gas pipeline transportation is disclosed, wherein the triazine compound is used as a natural gas drag reducer; the molecular structural formula of the triazine compound is shown as the formula (I):
in the formula (I), R is any one of cyclohexyl or phenyl.
2. Use according to claim 1, wherein the triazine is used by formulating it into an ethanol, gasoline, diesel or acetone solution.
3. The use according to claim 2, wherein the triazine compound is present in the solution prepared in an amount of 5 to 200 g/L.
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| CN105175402A (en) * | 2015-09-02 | 2015-12-23 | 陕西师范大学 | Synthetic method of 2-subsituted-4,6-dithienyl-1,3,5-s-triazine compounds |
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| TWI382983B (en) * | 2008-06-13 | 2013-01-21 | Univ Nat Chi Nan | A triazine derivative, a bis-triazine derivative for preparing the triazine derivative, and a polymer obtained by using the triazine derivative |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105175402A (en) * | 2015-09-02 | 2015-12-23 | 陕西师范大学 | Synthetic method of 2-subsituted-4,6-dithienyl-1,3,5-s-triazine compounds |
Non-Patent Citations (1)
| Title |
|---|
| "Solvent-free synthesis of melamines under microwave irradiation";Vanya B. Kurteva，等;《Green Chem .》;20041231;第6卷;第183-187页 * |
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