CN111377959A - 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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- CN111377959A CN111377959A CN201811652333.7A CN201811652333A CN111377959A CN 111377959 A CN111377959 A CN 111377959A CN 201811652333 A CN201811652333 A CN 201811652333A CN 111377959 A CN111377959 A CN 111377959A
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- phosphorus oxychloride
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 74
- 239000003345 natural gas Substances 0.000 title claims abstract description 40
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 19
- 239000010452 phosphate Substances 0.000 title claims abstract description 19
- 238000001308 synthesis method Methods 0.000 title claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 47
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- -1 phosphate ester Chemical class 0.000 claims description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
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- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 5
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- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 6
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 3
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 3
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- 239000000523 sample Substances 0.000 description 3
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- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 2
- 229940043375 1,5-pentanediol Drugs 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
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- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
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- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 238000001394 phosphorus-31 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
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- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
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- SCPWMSBAGXEGPW-UHFFFAOYSA-N dodecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OC)(OC)OC SCPWMSBAGXEGPW-UHFFFAOYSA-N 0.000 description 1
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- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- DNQXZHGDJABHGT-UHFFFAOYSA-N octadecylazanium phosphate Chemical compound [O-]P([O-])([O-])=O.CCCCCCCCCCCCCCCCCC[NH3+].CCCCCCCCCCCCCCCCCC[NH3+].CCCCCCCCCCCCCCCCCC[NH3+] DNQXZHGDJABHGT-UHFFFAOYSA-N 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
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- 150000004032 porphyrins Chemical class 0.000 description 1
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- 239000011780 sodium chloride Substances 0.000 description 1
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- 229910052717 sulfur Inorganic materials 0.000 description 1
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- 239000012085 test solution Substances 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical group C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 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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- Chemical & Material Sciences (AREA)
- 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)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- General Engineering & Computer Science (AREA)
Abstract
The invention discloses a phosphate oligomer natural gas drag reducer and a synthetic 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 R1OH solution to generate phosphorus oxychloride monosubstituted product. Raising the temperature and dropwise adding diol HOR2OH, generating phosphorus oxychloride oligomer. Increasing the temperature, adding alcohol R3And OH, obtaining a crude product. And after the reaction is finished, washing and removing the solvent to obtain the product. The drag reducer has good adsorptivityCan achieve excellent drag reduction and output 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, 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.
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 ammonium phosphate), unobvious drag reduction effect, and poor solubility (such as hexatomic ring alkyl siloxane-phosphate), which cannot be applied to natural gas pipeline drag reduction in a 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 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):
in the formula (I), R1Is greater than or equal to C4A chain hydrocarbon of (3), an aromatic hydrocarbon, a fatty alcohol-polyoxyethylene ether (RO (CH)2CH2O)mH, R is greater than C7M is more than 5), R2Is C2-C6Any one of chain or aromatic hydrocarbons, R3Is 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 C1Controlling the dripping speed of the OH solution to ensure 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) dropwise adding diol HOR into the system in the step (1) at 10-30 DEG C2OH, 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 C3OH, enabling the temperature of a reaction system to be not higher than 60 ℃, raising the temperature, and reacting for 3-6 hours 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 R1The molar ratio of OH is 1: 0.8-1: 1.5, the molar ratio of phosphorus oxychloride to catalyst is 1: 0.01-1: 1, phosphorus oxychloride with diol HOR2The molar ratio of OH is 1: 0.8-1: 1.5 phosphorus oxychloride with diol R3The molar ratio of OH is 1: 0.3-1: 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)1OH may be a carbon chain greater than C4Alcohol, aromatic alcohol, fatty alcohol-polyoxyethylene ether (RO (CH)2CH2O)mH, R is greater than C7M is greater than 5).
In the present invention, the diol HOR described in the step (2)2OH may be C2-C6Alcohol or aromatic alcohol.
In the present invention, the alcohol R in the step (3)3OH 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 for the phosphate ester oligomer drag reducer of the present invention is as follows:
the third aspect of the invention also provides a use of the aforementioned phosphate ester 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 nonpolar group composed of an atom having a large electronegativity, such as N, P, O, S, as a central polar group and C, 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 existing 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 transmission 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 of the antifreeze solution in field application and added into a pipeline without 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 11HNMR spectrogram.
FIG. 2 is a drawing of a drag reducer obtained in example 131P NMR spectrum.
FIG. 3 is an SEM of the surface of a blank steel sheet and a steel sheet after spraying a drag reducer. Wherein, (a) a blank steel surface; (b) the steel surface after film forming; (c) and (5) treating the surface of the steel by using 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 (400MHz) NMR spectrometer, Germany1Nuclear magnetic spectrum of H with CDCl3The solution is a solvent, the concentration of the solution is 10-25%, and the internal standard substance is tetramethylsilane; the soaked sample was subjected to scanning test using a FEI QUANTA-200(Eindhoven, Netherlands) type scanning electron microscope at an acceleration voltage of15 kV; the polymerization degree of the product is tested and analyzed by adopting an Agilent Q-TOF 2105-6520 (USA) mass spectrometer; performing electrochemical test and data analysis on the tested sample by using 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 2 h. 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 reducer1And (5) HNMR test results. As can be seen from the graph, the peak at 0.91 to 0.96ppm in the graphIs 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 analysis of the data shows that the product is the target compound designed and synthesized by the people.
FIG. 2 shows the obtained product31P 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 deep surface indentation and a large roughness, and the gas flowing through the surface is affected by a large resistance (fig. 3-a). The indentations on the surface of the steel sheet after the drag reducer coating (fig. 3-b) 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, 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. 4 is the electrochemical impedance spectrum of the 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. 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 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.
FIG. 5 and Table 1 show the results of electrochemical polarization curve tests after film formation of blank electrode and drag reducer, from which it can be seen that the cathodic polarization curve does not change significantly compared to the blank iron electrode, the anodic polarization curve becomes steep under the protection of the drag reducer, the value of the self-corrosion potential increases from-0.644V to-0.512V and increases by 0.132V, and the self-corrosion current increases from 1.35 × 10-5A is reduced to 0.47 × 10-5A, reduced by 0.88 × 10-5A. 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 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 25 ℃ and the reaction is carried out for 4 h. 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 87.7 wt%.
The structural formula of the product obtained in this embodiment is as follows:
wherein n = 2-6.
By passing1HNMR, the structure of the product was determined. Indoor loop test and analysis show that the product is preparedThe mixture 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 4 h. Slowly dripping 104.2g of 1, 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 raised to 60 ℃ and the reaction is carried out for 7 h. 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 to remove the solvent, to give 222.3g of a pale yellow viscous liquid with a yield of 88.9 wt%.
The structural formula of the product obtained in this embodiment is as follows:
wherein n = 3-8.
By passing1HNMR, 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 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-5 to 5 ℃. The temperature is increased to 20 ℃ and the reaction is carried out for 4 h. 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 to remove the solvent, to give 617.9g of a pale yellow viscous liquid with a yield of 86.3 wt%.
The structural formula of the product obtained in this embodiment is as follows:
wherein n = 3-7.
By passing1HNMR, 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 30g/L, the average drag reduction rate can reach 10.8%, and the effective period is more than 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-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-5 ℃. The temperature is increased to 20 ℃ and the reaction is carried out for 4 h. 118.2g of 1, 6-hexanediol is slowly dripped at the temperature of 20 ℃, the temperature of the system is controlled not to exceed 30 ℃, the reaction is carried out for 2 hours at the temperature of 30 ℃, the temperature is raised to 60 ℃, and the reaction is carried out 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 passing1HNMR, the structure of the product was determined. Indoor loop test analysis shows that the product is prepared into ethanol solution, atomized and injected into the loop, the test pressure is 0.5-0.6MPa, and when the concentration of the drag reducer is 35g/L, the average drag reducer is reducedThe resistivity can reach 10.1 percent, and the effective period is more than 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 4 h. 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 passing1HNMR, 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 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 the reaction was carried out for 7 hours. 90.1g of 1, 4-butanediol were added dropwise at 20 ℃ and reacted for 10 h. 12.0g of n-propanol were added at 50 ℃ and reacted for 6 h. The crude product was washed with water to remove the solvent, yielding 488.3g of a pale yellow viscous liquid with a yield of 68.2 wt%.
The structural formula of the product obtained in this embodiment is as follows:
wherein n = 0-4.
By passing1HNMR, 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 60g/L, the average drag reduction rate can reach 8.0%, and the effective period is more than 60 days.
Claims (14)
1. A phosphate ester oligomer natural gas drag reducer has a molecular structural formula shown as a formula (I):
in the formula (I), R1Is greater than or equal to C4The chain hydrocarbon of (A), aromatic hydrocarbon, fatty alcohol polyoxyethylene ether RO (CH)2CH2O)mAny one of H, R2Is C2-C6Any one of chain or aromatic hydrocarbons, R3Is aliphatic hydrocarbon, and n is any integer of 2-9.
2. The natural gas drag reducer of claim 1, wherein said fatty alcohol-polyoxyethylene ether RO (CH)2CH2O)mIn H, R is a hydrocarbyl group larger than C7, and m is an integer larger than 5.
3. The process for synthesizing the phosphate ester oligomer natural gas drag reducer of claim 1 or 2, comprising the following:
(1) dissolving phosphorus oxychloride and a catalyst in a solvent, and dropwise adding alcohol R at-10-0 DEG C1Controlling the dripping speed of the OH solution to enable the temperature of a reaction system to be not higher than 0 ℃, reacting for 2-4 hours at-10-5 ℃, and heating to 10-30 ℃ for reacting for 2-4 hours;
(2) dripping glycol HOR at 10-30 DEG C2OH, controlling the dropping speed to ensure that the temperature of the reaction system is not higher than 30 ℃, andreacting for 2-4 h at 10-30 ℃, heating to 30-60 ℃ and reacting for 4-10 h;
(3) dripping alcohol R at 50-60 DEG C3OH, enabling the temperature of a reaction system to be not higher than 60 ℃, raising the temperature, and reacting for 3-6 hours at the temperature of 60-120 ℃;
(4) stopping the reaction, washing the crude product, and removing the solvent to obtain the final product.
4. A synthesis process according to claim 3, characterized in that the alcohol R is1OH is carbon chain greater than or equal to C4Alcohol of (A), aromatic alcohol, fatty alcohol polyoxyethylene ether (RO (CH)2CH2O)mH, R is greater than C7M is greater than 5).
5. A synthesis method according to claim 3, characterized in that said diol HOR2OH is C2-C6Alcohol or aromatic alcohol.
6. A synthesis process according to claim 3, characterized in that the alcohol R is3OH is any one of fatty alcohols.
7. The synthesis method according to claim 3, wherein the solvent is selected from one or more of ethers, ketones, toluene and xylene.
8. A process according to claim 3, characterized in that phosphorus oxychloride together with the alcohol R1The molar ratio of OH is 1: 0.8-1: 1.5, preferably 1: 0.9-1: 1.1; the molar ratio of the phosphorus oxychloride to the catalyst is 1: 0.01-1: 1, preferably 1: 0.03 to 1: 0.5.
9. a process according to claim 3, characterized in that phosphorus oxychloride with the diol HOR2The molar ratio of OH is 1: 0.8-1: 1.5, preferably 1: 0.9-1: 1.1.
10. a process according to claim 3, characterized in that phosphorus oxychloride together with the alcohol R3The molar ratio of OH is 1: 0.1-1: 1, preferably 1: 0.2-1: 0.4.
11. the synthesis method according to claim 3, wherein the catalyst is one or more of triethylamine, ethylenediamine, pyridine, piperidine, N-diisopropylethylamine, anhydrous aluminum chloride and anhydrous magnesium chloride, and preferably anhydrous aluminum chloride and/or anhydrous magnesium chloride.
12. Use of the phosphate ester oligomer drag reducer of claim 1 or 2 in natural gas pipeline transportation.
13. The use according to claim 12, wherein the phosphate ester oligomer drag reducing agent is formulated as an ethanol, gasoline, diesel or acetone solution for drag reduction and flow enhancement in natural gas pipelines.
14. The use according to claim 13, wherein the phosphate ester oligomer natural gas drag reducer is present in the formulated solution in an amount of 10 to 120 g/L.
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Effective date of registration: 20231116 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |