CN111377959B - Phosphate oligomer natural gas drag reducer and synthesis method and application thereof - Google Patents
Phosphate oligomer natural gas drag reducer and synthesis method and application thereof Download PDFInfo
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- CN111377959B CN111377959B CN201811652333.7A CN201811652333A CN111377959B CN 111377959 B CN111377959 B CN 111377959B CN 201811652333 A CN201811652333 A CN 201811652333A CN 111377959 B CN111377959 B CN 111377959B
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- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 73
- 239000003345 natural gas Substances 0.000 title claims abstract description 41
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 18
- 239000010452 phosphate Substances 0.000 title claims abstract description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims description 12
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical group C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
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- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/12—Esters of phosphoric acids with hydroxyaryl compounds
-
- 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
- C23F11/167—Phosphorus-containing compounds
- C23F11/1673—Esters of phosphoric or thiophosphoric acids
-
- 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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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
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Abstract
The invention discloses a phosphate ester oligomer natural gas drag reducer and a synthesis method thereof. The molecular structural formula is as follows:
. The drag reducer is synthesized by the following method: dissolving phosphorus oxychloride and a catalyst in a solvent, and dropwise adding alcohol R 1 OH solution to generate phosphorus oxychloride monosubstituted product. Raising the temperature and dropwise adding diol HOR 2 OH, generating phosphorus oxychloride oligomer. Increasing the temperature, adding alcohol R 3 And OH, obtaining a crude product. And after the reaction is finished, washing and removing the solvent to obtain the product. The drag reducer of the invention has good adsorption performance and excellent drag reduction and delivery increase effects. The invention has the advantages of simple synthesis process, mild condition, short reaction 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 phosphate oligomer natural gas drag reducer and a synthetic method thereof.
Background
In recent years, the demand of natural gas in China is gradually increased, part of pipelines reach a full-load operation state, and the pipeline output is further increased due to seasonal peak regulation requirements in part of regions. For in-service pipelines, the pressurization operation is the most direct and effective method for improving the pipeline output, but the pressurization transformation cost is high, the period is long, and the implementation difficulty is high.
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 on-way pressure drop 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. The main methods for reducing drag and increasing output are an inner coating drag reduction technology and a drag reducer drag reduction technology. In recent years, natural gas pipeline drag reduction conveying becomes a research hotspot at home and abroad, and by reducing pipeline friction and inhibiting radial pulsation, the aims of reducing on-way pressure drop and energy loss, reducing conveying pressure and improving conveying efficiency are achieved, and meanwhile, the safety risk caused by pipeline pressurization can also be reduced. At present, natural gas drag reduction conveying has not been industrially applied, but has shown huge economic value and application potential. Therefore, the research on the natural gas drag reduction conveying process technology has important significance for improving the flowability of natural gas, improving the pipe conveying efficiency and guaranteeing the safe operation of a pipeline, and simultaneously has better actual production requirements and market prospects.
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, so that the radial pulsation of the gas and the pulsation generated by the rough bulges are reduced, the vortex energy is reduced, and the flow resistance is reduced, thereby achieving the aim of reducing drag. 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 the nitrogen-containing natural gas drag reducer is used for drag reduction and transportation increase of a gas pipeline. CN 102040908A discloses a method for synthesizing dodecyl trimethoxy silane drag reducer by taking trimethoxy silane and alpha-dodecene as raw materials and in the presence of a platinum catalyst. The Mannich alkali type drag reducer synthesized by the patent CN 101328442A through a two-step method can be applied to drag reduction and transportation increase of natural gas gathering and transportation pipelines.
In addition, there are some reports on the synthesis of nitrogen-containing drag reducers, such as patent CN 102838606A also discloses the preparation of a porphyrin-based natural gas drag reducer, and patent CN 101575497A; US 5549848A; CN 101328441A; CN 101329011A; w.g. Xing et al (polymer. Degrad. Stab. 2011, 92; yetiana et al (Natural gas industry 2010, 30. Patents CN 102443022A and CN 102863473A report phosphorous-containing drag reducing agents octodecyl alcohol phosphate ammonium salts and six-membered cycloalkyl siloxane-phosphates, respectively.
According to the existing drag reduction mechanism and reported field experiments, the drag reduction effect of the organic phosphorus compound is expected to be better. However, the currently reported patents and documents have some defects, mainly including single polar end, weak adsorbability, few non-polar ends (such as octadecyl alcohol phosphate ammonium salts), unobvious drag reduction effect, poor solubility (such as hexatomic cycloalkyl siloxane-phosphate esters), and incapability of being applied to drag reduction of natural gas pipelines on a large scale, so that the application range is greatly limited, and the drag reduction effect needs to be further improved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a phosphate oligomer natural gas drag reducer and a synthetic method thereof. The drag reducer of the present invention has an excellent drag reduction effect. The synthesis method is simple, short in reaction time and easy for industrial production.
The invention provides a phosphate oligomer natural gas drag reducer, which has a molecular structural formula shown as a formula (I):
formula (I);
in the formula (I), R 1 Is greater than or equal to C 4 A chain hydrocarbon, an aromatic hydrocarbon, fatty alcohol-polyoxyethylene ether (RO (CH) 2 CH 2 O) m H, R is greater than C 7 M is more than 5), R 2 Is C 2 -C 6 Any one of chain or aromatic hydrocarbons, R 3 Is an aliphatic hydrocarbon, n =2-9.
The second aspect of the invention also provides a method for synthesizing the phosphate ester oligomer drag reducer. The method comprises the following steps:
(1) Dissolving phosphorus oxychloride and a catalyst in a solvent, and dropwise adding alcohol R at-10-0 DEG C 1 The dripping speed of the OH solution is controlled, so that the temperature of a reaction system is not higher than 0 ℃; reacting for 2-4 h at-10-5 ℃, and heating to 10-30 ℃ for reacting for 2-4 h;
(2) Adding diol HOR dropwise into the system in the step (1) at 10-30 DEG C 2 OH, controlling the dropping speed to ensure that the temperature of a reaction system is not higher than 30 ℃; after the dropwise adding is finished, reacting for 2-4 h at 10-30 ℃, and heating to 30-60 ℃ for reacting for 4-10 h;
(3) Dripping alcohol R at 50-60 DEG C 3 OH, raising the temperature of a reaction system to be not higher than 60 ℃, and reacting for 3-6 h at the temperature of 60-120 ℃;
(4) Stopping the reaction, washing the crude product, and removing the solvent to obtain the final product.
In the present invention, phosphorus oxychloride and alcohol R 1 The molar ratio of OH is 1:0.8 to 1:1.5, the molar ratio of phosphorus oxychloride to catalyst is 1:0.01 to 1:1, phosphorus oxychloride with diol HOR 2 The molar ratio of OH is 1:0.8 to 1:1.5 phosphorus oxychloride with diol R 3 The molar ratio of OH is 1:0.3 to 1:0.6.
the catalyst is one or more of triethylamine, ethylenediamine, pyridine, piperidine, N-diisopropylethylamine, anhydrous aluminum chloride and anhydrous magnesium chloride.
Alcohol R described in step (1) 1 OH may be a carbon chain greater than C 4 Alcohol, aromatic alcohol, fatty alcohol-polyoxyethylene ether (RO (CH) 2 CH 2 O) m H, R is greater than C 7 M is greater than 5).
In the present invention, in the step (2)The diol HOR 2 OH may be C 2 -C 6 Alcohol or aromatic alcohol.
In the present invention, the alcohol R in the step (3) 3 OH is any one of fatty alcohols.
The solvent in the step (1) can be one or more of ethers, ketones, toluene and xylene.
The washing described in step (4) is a routine operation for those skilled in the art, and may be washed with deionized water.
The synthetic route of the phosphate ester oligomer drag reducer of the invention is as follows:
the third aspect of the invention also provides the use of the aforementioned phosphate oligomer drag reducer, i.e., the use of the drag reducer in natural gas pipeline transportation.
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 for drag reduction and transportation increase of natural gas pipelines. The content of the phosphate oligomer natural gas drag reducer in the prepared solution is generally 10-120 g/L.
The natural gas drag reducer synthesized by the invention can reduce gas transmission power, improve gas transmission capacity and meet the requirement of seasonal peak regulation in pipeline transportation, and reduces the danger of full-load operation to a certain extent. In addition, the synthesized drag reducer can also play an auxiliary function of corrosion inhibition and the like.
Besides, the product of the invention also has a certain corrosion inhibition function on the natural gas pipeline.
Compared with the prior art, the phosphate oligomer natural gas drag reducer has the following characteristics:
1. at present, the mechanism in the field of natural gas pipeline drag reducers is not well established, but researchers generally believe it to be similar to the corrosion inhibitor mechanism. The applicant believes that a drag reducer having excellent performance is generally composed of a polar group having as a center an atom of N, P, O, S, or the like having a large electronegativity and a nonpolar group composed of C and H atoms. The polar gene is adsorbed on the metal surface, so that the double electric layer structure of the metal surface is changed, the activation energy of metal ionization is improved, the non-polar group forms a flexible chain segment on the metal surface, and the polar gene and the non-polar group have the effects of resistance reduction and output increase under the combined action. The drag reducer overcomes the defects of poor adsorptivity and short duration of drag reduction effect of the conventional natural gas drag reducer.
2. The phosphate oligomer natural gas drag reducer is a compound with a good adsorption effect, is used as a drag reduction additive of a natural gas pipeline, is atomized, 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 pipeline metal, and forms a smooth film, while the non-polar end exists between the pipeline fluid and the inner surface, part of the drag reduction additive fills the recess of the inner surface of the pipeline, reduces the roughness, the non-polar end is suspended in the airflow downstream under the action of shear stress, part of the energy of impacting the inner wall fluid molecules is absorbed and returned to the fluid in the process of recovering and stretching the molecules, the radial pulsation of the gas and the pulsation generated by rough protrusions are reduced, and simultaneously the vortex energy is reduced. The product of the invention is light yellow viscous liquid, and has good adsorption performance and excellent drag reduction and output increase effects on the metal surface.
3. The synthesis method provided by the invention is based on molecular structure analysis of a drag reducer product, three-stage reaction is adopted in the reaction process, three chlorine atoms in phosphorus oxychloride are gradually substituted, and the reaction conditions are controlled in a segmented manner when one chlorine atom is substituted, so that the occurrence of side reaction in each step of substitution reaction is inhibited or reduced, and the yield of the final target product is improved; at the same time, the degree of polymerization of the oligomer is also increased. The drag reducer provided by the invention has the advantages of simple synthesis process, mild reaction conditions, short reaction time and synthesis yield of more than 85%. Meanwhile, the synthesis process has low requirements on equipment, and is easy to realize large-scale industrial production, so the method has good popularization prospect.
4. The drag reducer product has good solubility in methanol and ethanol, can be directly dissolved with the methanol as an antifreeze solution in a pipeline in field application, and does not need to be subjected to other treatment. Moreover, the addition amount of the drag reducer in methanol or ethanol is small, and the addition amount of most products is less than 50g/L, so that an ideal drag reduction effect can be achieved; the adsorbability is strong, and the longest effective time can be more than 90 days; the atomization is easy in the filling process, and the dispersion and the adsorption on the inner wall of the pipeline can be better realized.
Drawings
FIG. 1 is a drawing showing a drag reducer obtained in example 1 1 HNMR spectrogram.
FIG. 2 is a drawing of a drag reducer obtained in example 1 31 P NMR spectrum.
FIG. 3 is an SEM of the blank sheet and the surface of the sheet after spraying the drag reducer. Wherein, (a) a blank steel surface; (b) the steel surface after film formation; (c) treating the surface of the steel with the condensate.
FIG. 4 is an electrochemical impedance spectrum of a blank iron electrode and the iron electrode after film formation of the drag reducing agent of example 1.
Fig. 5 is an electrochemical polarization curve of the electrode and the blank electrode after the film formation of the drag reducer in example 1.
Detailed Description
The phosphate oligomer natural gas drag reducer of the present invention and the process for its preparation are further illustrated by the following examples, which are intended to be illustrative only and not limiting.
The products tested in the examples were tested using a Bruker 400 (400 MHz) NMR spectrometer, germany 1 Nuclear magnetic spectrum of H with CDCl 3 Is a solvent, the concentration of the solution is 10 to 25 percent, and the internal standard substance is tetramethylsilane; scanning the soaked sample by using an FEI QUANTA-200 (Eindhoven, netherlands) type scanning electron microscope, wherein the acceleration voltage is 15kV; testing and analyzing the polymerization degree of the product by using an Agilent Q-TOF 2105-6520 (USA) mass spectrometer; performing electrochemical test and data analysis on the tested sample by adopting an IM6 electrochemical workstation of Germany ZAHZER company; the used indoor loop test evaluation device is a self-made test device.
Phosphorus oxychloride (analytically pure) used in the examples was purchased from Tianjin department Mi Euro chemical reagent development center, anhydrous aluminum chloride, anhydrous magnesium chloride, pyridine, triethylamine, N-diisopropylethylamine (all analytically pure) was purchased from Shanghai Alantin Biotechnology GmbH, methyl ethyl ketone, butyl ether, 2-pentanone, toluene, ethylene glycol diethyl ether, N-butanol, ethylene glycol, ethanol, N-octanol, hexanediol, N-heptanol, N-hexanol, 1, 5-pentanediol, 1, 4-butanediol, N-propanol, 1, 6-hexanediol, phenol (all analytically pure) was purchased from Tianjin Mao chemical reagent factory, and AEO-9 and AEO-7 (all industrial grade) were purchased from Shenyang reagent five factory.
Example 1
153.3g of phosphorus oxychloride, 1.33g of anhydrous aluminum trichloride and 600mL of methyl ethyl ketone are added into a 3000mL four-mouth bottle provided with a reflux condenser, a thermometer, a stirrer and a constant-pressure dropping funnel, the four-mouth bottle is cooled to-10 ℃ and maintained for 20min, 74.1g of n-butanol is slowly dropped into the bottle under stirring, and the temperature of the system is controlled not to exceed 0 ℃. And reacting for 2 hours at the temperature of-5 to 5 ℃. The temperature is increased to 20 ℃ and the reaction is carried out for 2h. Slowly dropwise adding 62.1g of ethylene glycol at 20 ℃, controlling the temperature of the system to be not more than 30 ℃, reacting for 2 hours at 30 ℃, heating to 50 ℃, and reacting for 4 hours. 9.2g of ethanol is added at 50 ℃ and the reaction is carried out for 4 hours under reflux, and the reaction is finished when the pH value of the solution is close to neutral. The crude product was washed with water and the solvent was removed to give 161.3g of a pale yellow viscous liquid in 89.6% by weight yield.
The structural formula of the product obtained in this embodiment is as follows:
wherein n =4-9.
FIG. 1 is of a drag reducer 1 And (5) HNMR test results. As can be seen from the figure, the peak at 0.91 to 0.96ppm in the figure is the chemical shift of a proton on the terminal methyl group in n-butanol; the peak at 1.22 to 1.29ppm is the chemical shift of the b proton on the terminal methyl group in ethanol; and peaks at 1.55 to 1.61ppm and 1.77 to 1.85ppm are attributed to the chemical shifts of the c and d protons on the methylene group in n-butanol, respectively; the peak at 4.03 to 4.14ppm is due to the chemical shift of the e proton on the methylene group attached to the oxygen; the chemical shift of the f proton in ethylene glycol is located at 4.42 to 4.49 ppm. The above data analysis shows that the product is the purpose of the designed synthesisA target compound.
FIG. 2 shows the product obtained 31 P NMR spectrum with only one peak at 13.1ppm, indicating that all the phosphorus atoms in the chemical structure are in the same chemical environment and that the chemical shift of the phosphorus atom occurs at 13.1ppm for the product.
And (5) testing film forming property and stability. FIG. 3 is an SEM of the surface of a blank steel sheet and a steel sheet after spraying a drag reducer. As can be seen from fig. 3, the blank sheet has a deeper indentation and a greater roughness on the surface, and the gas flow through its surface is affected by a greater resistance (fig. 3-a). The indentations on the surface of the steel sheet (fig. 3-b) after coating with the drag reducer are filled more uniformly with the product. The drag reducer forms a layer of compact protective film on the surface of the steel sheet, so that the surface of the steel sheet becomes smoother, and the roughness of the steel sheet is greatly reduced. The experimental result shows that the product has good film-forming property on the steel surface and has the properties required by the natural gas drag reducer. FIG. 3-c shows an SEM image of the experimental back surface of the as-coated steel sheet in the as-prepared simulated condensate. It can be seen that the steel sheet surface treated with the condensate had some dimples visible, but the roughness was still reduced compared to the blank sheet, and a certain amount of the drag reducing agent product was still adsorbed in the dimples. The experimental result shows that although the roughness of the steel sheet is increased compared with that of a sample which is not subjected to suspected liquid system scouring after the steel sheet is stirred in the simulated condensate liquid for 30 days, the drag reducer has no obvious chemical change in the simulated condensate liquid system, and the synthesized drag reducer still has good film forming stability on the surface of the steel sheet.
And (4) performing electrochemical test. The iron electrode (Q235) was encapsulated with epoxy resin, 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 was used, the working electrode was an iron electrode, the reference electrode was a saturated calomel electrode, the platinum electrode was an auxiliary electrode, a sinusoidal perturbation signal with an amplitude of 5mV was selected, the signal was scanned from high to low frequencies in the frequency range of 0.02Hz-60kHz, and electrochemical impedance spectroscopy was performed 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. 4 is the electrochemical impedance spectrum of the blank iron electrode and the film-formed iron electrode. 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. 4, 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 reactance arcs are formed from a high-frequency area to a low-frequency area. The capacitive reactance arc formed in the high-frequency area is the capacitive reactance arc formed by film formation of the drag reducer, which indicates that the drag reducer forms a barrier film on the surface of the iron electrode, and then forms a larger capacitive reactance arc in the low-frequency area, and is the capacitive reactance arc of the iron electrode after film formation, the diameter of the capacitive reactance arc is larger than that of a blank iron electrode, because the blocking effect of the iron electrode with the protective film on a medium is larger, the medium on the surface of the iron electrode is reduced, so that the charge transfer resistance is larger, and the synthesized drag reducer has good film forming performance on the surface of the iron.
Fig. 5 and table 1 show the electrochemical polarization curve test results after film formation of the blank electrode and the drag reducer. As can be seen from the results, compared with a blank iron electrode, the change of the cathodic polarization curve is not obvious, the anodic polarization curve becomes steep under the protection of the drag reducer, the self-corrosion potential value is increased from-0.644V to-0.512V and is increased by 0.132V, and the self-corrosion current is increased from 1.35 multiplied by 10 -5 A is reduced to 0.47 × 10 -5 A, is reduced by 0.88 × 10 -5 A. The electrochemical polarization curve test result shows that the drag reducer can form a stable protective film on the surface of the iron electrode to block the interaction between the electrode and the test solution, so that the iron electrode is more stable, the self-corrosion potential is increased, and the self-corrosion current is reduced. The film forming process of the synthesized drag reducer belongs to an anode control type, and a product forms a film on the surface of an anode.
Table 1 electrochemical polarization test results of the electrodes and blank electrodes after film formation.
Indoor loop test analysis shows that the product is prepared into ethanol solution and atomized and injected into the loop. The testing pressure is 0.5-0.6MPa, when the concentration of the drag reducer is 30g/L, the average drag reduction rate can reach 8.5%, and the effective period exceeds 60 days.
Example 2
153.3g of phosphorus oxychloride, 1.9g of anhydrous magnesium chloride and 600mL of butyl ether are added into a 3000mL four-mouth bottle provided with a reflux condenser, a thermometer, a stirrer and a constant-pressure dropping funnel, the four-mouth bottle is cooled to-10 ℃ and maintained for 20min, 130.2g of n-octanol is slowly dropped into the bottle while stirring, the temperature of the system is controlled not to exceed 0 ℃, and the reaction is carried out for 3h at-5 ℃. The temperature is increased to 25 ℃ and the reaction is carried out for 4h. Slowly dripping 118.2g butyl ether solution of hexanediol at 25 ℃, controlling the temperature of the system to be not more than 30 ℃, reacting for 3 hours at 30 ℃, heating to 50 ℃, and reacting for 8 hours. 23.2g of n-heptanol is added at 50 ℃, the reaction is refluxed for 6 hours, and the reaction is finished when the pH value of the solution is close to neutral. The crude product was washed with water to remove the solvent, to give 257.0g of a pale yellow viscous liquid with a yield of 87.7wt%.
The structural formula of the product obtained in this embodiment is as follows:
wherein n =2-6.
By passing 1 HNMR, the structure of the product was determined. 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 9.2%, and the effective period is more than 60 days.
Example 3
153.3g of phosphorus oxychloride, 7.9g of pyridine and 600mL of 2-pentanone are added into a 3000mL four-mouth bottle provided with a reflux condenser, a thermometer, a stirrer and a constant-pressure dropping funnel, the four-mouth bottle is cooled to-10 ℃ and maintained for 20min, 102.2g of n-hexanol is slowly dropped into the bottle under stirring, the temperature of the system is controlled not to exceed 0 ℃, and the reaction is carried out for 3h at-5 ℃. The temperature is increased to 30 ℃ and the reaction is carried out for 4h. Slowly dripping 104.2g1, 5-pentanediol at the temperature of 30 ℃, controlling the temperature of the system to be about 30 ℃, and reacting for 4 hours; the temperature is increased to 60 ℃ and the reaction is carried out for 7h. 14.8g of n-butanol is added at 60 ℃ and the reaction is refluxed for 5 hours, and the reaction is finished when the pH value of the solution is close to neutral. The crude product was washed with water and the solvent was removed to give 222.3g of a pale yellow viscous liquid with a yield of 88.9wt%.
The structural formula of the product obtained in this embodiment is as follows:
wherein n =3-8.
By passing 1 HNMR, which determined the structure of the product. 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 8.5%, and the effective period is more than 60 days.
Example 4
153.3g of phosphorus oxychloride, 10.1g of triethylamine and 600mL of toluene are added into a 3000mL four-mouth bottle provided with a reflux condenser, a thermometer, a stirrer and a constant-pressure dropping funnel, the four-mouth bottle is cooled to-10 ℃ and maintained for 20min, 582.0g of AEO-9 is slowly dropped into the bottle while stirring, and the temperature of the system is controlled not to exceed 0 ℃. And reacting for 3 hours at the temperature of minus 5 to 5 ℃. The temperature is increased to 20 ℃ and the reaction is carried out for 4h. Slowly dripping 90.1g of 1, 4-butanediol at 20 ℃, controlling the temperature of the system not to exceed 30 ℃, reacting for 2 hours at 30 ℃, heating to 50 ℃ and reacting for 8 hours. 12.0g of n-propanol was added at 50 ℃ and the reaction was refluxed for 6 hours, and the reaction was terminated when the pH of the solution was close to neutral. The crude product was washed with water and the solvent was removed to give 617.9g of a pale yellow viscous liquid in 86.3wt% yield.
The structural formula of the product obtained in this embodiment is as follows:
wherein n =3-7.
By passing 1 HNMR, which determined the structure of the product. 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 30g/L, the average drag reduction rate can reach 10.8%, and the effective period exceeds 60 days.
Example 5
153.3g of phosphorus oxychloride, 15.5g of N, N-diisopropylethylamine and 600mL of ethylene glycol diethyl ether are added into a 3000mL four-mouth bottle provided with a reflux condenser, a thermometer, a stirrer and a constant-pressure dropping funnel, the four-mouth bottle is cooled to minus 10 ℃ and maintained for 20min, 538.0g of AEO-7 is slowly dropped into the bottle under stirring, the temperature of the system is controlled not to exceed 0 ℃, and the reaction is carried out for 3h at minus 5-5 ℃. The temperature is increased to 20 ℃ and the reaction is carried out for 4h. Slowly dripping 118.2g1, 6-hexanediol at 20 ℃, controlling the temperature of the system to be not more than 30 ℃, reacting for 2 hours at 30 ℃, heating to 60 ℃ and reacting for 8 hours. Adding 20.4g of n-hexanol at 60 ℃, and carrying out reflux reaction for 6h, wherein the reaction is finished when the pH value of the solution is close to neutral. The crude product was washed with water and the solvent was removed to give 578.0g of a pale yellow viscous liquid in 87.8% by weight yield.
The structural formula of the product obtained in this embodiment is as follows:
wherein n =2-5.
By passing 1 HNMR, the structure of the product was determined. 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 35g/L, the average drag reduction rate can reach 10.1%, and the effective period exceeds 60 days.
Example 6
153.3g of phosphorus oxychloride, 10.1g of triethylamine and 600mL of toluene are added into a 3000mL four-mouth bottle provided with a reflux condenser, a thermometer, a stirrer and a constant-pressure dropping funnel, the four-mouth bottle is cooled to-10 ℃ and maintained for 20min, 94.1g of phenol is slowly added under stirring, the temperature of the system is controlled not to exceed 0 ℃, and the reaction is carried out for 4h at-5 ℃. The temperature is increased to 20 ℃ and the reaction is carried out for 4h. Slowly dropwise adding 62.1g of ethylene glycol at 20 ℃, controlling the temperature of the system to be not more than 30 ℃, reacting for 4 hours at 30 ℃, heating to 60 ℃, and reacting for 10 hours. 9.2g of ethanol is added at 60 ℃, the reflux reaction is carried out for 6 hours, and the reaction is finished when the pH value of the solution is close to neutral. The crude product was washed with water to remove the solvent, to give 164.4g of a pale yellow viscous liquid with a yield of 80.2 wt%.
The structural formula of the product obtained in this embodiment is as follows:
wherein n =2-7.
By passing 1 HNMR, which determined the structure of the product. 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 8.7%, and the effective period is more than 60 days.
Comparative example
153.3g of phosphorus oxychloride, 10.1g of triethylamine and 600mL of toluene 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-5 ℃ and maintained for 20min, and 582.0g of AEO-9 was added dropwise with stirring and reacted for 7 hours. 90.1g of 1, 4-butanediol were added dropwise at 20 ℃ and reacted for 10h. 12.0g of n-propanol were added at 50 ℃ and reacted for 6h. The crude product was washed with water to remove the solvent, yielding 488.3g of a pale yellow viscous liquid with a yield of 68.2wt%.
The structural formula of the product obtained in this embodiment is as follows:
wherein n =0-4.
By passing 1 HNMR, the structure of the product was determined. Indoor loop test analysis shows that the product is prepared into ethanol solution and atomized and injected into the loopThe testing pressure is 0.5-0.6MPa, when the concentration of the drag reducer is 60g/L, the average drag reduction rate can reach 8.0 percent, and the effective period exceeds 60 days.
Claims (4)
1. A phosphate ester oligomer natural gas drag reducer has a molecular structural formula shown as a formula (I):
2. Use of the phosphate oligomer natural gas drag reducer of claim 1 in natural gas pipeline transportation.
3. The use according to claim 2, wherein the phosphate ester oligomer natural gas drag reducer is formulated as an ethanol, gasoline, diesel or acetone solution for drag reduction and transportation enhancement of natural gas pipelines.
4. The use according to claim 3, wherein the phosphate oligomer natural gas drag reducer is present in the formulated solution in an amount of 10 to 120g/L.
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