CN116655914A - Degradable bio-based scale inhibitor and preparation method and application thereof - Google Patents
Degradable bio-based scale inhibitor and preparation method and application thereof Download PDFInfo
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- 239000002455 scale inhibitor Substances 0.000 title claims abstract description 136
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 17
- 235000013922 glutamic acid Nutrition 0.000 claims description 17
- 239000004220 glutamic acid Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
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- 159000000009 barium salts Chemical class 0.000 claims description 2
- 159000000007 calcium salts Chemical class 0.000 claims description 2
- 159000000003 magnesium salts Chemical class 0.000 claims description 2
- 230000005764 inhibitory process Effects 0.000 abstract description 79
- 229920000805 Polyaspartic acid Polymers 0.000 abstract description 46
- 108010064470 polyaspartate Proteins 0.000 abstract description 46
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- 239000000126 substance Substances 0.000 abstract description 7
- 229920000642 polymer Polymers 0.000 abstract description 5
- 238000012216 screening Methods 0.000 abstract description 4
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- 101000946524 Homo sapiens Carboxypeptidase B Proteins 0.000 abstract 1
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- 239000000047 product Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
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- 239000008398 formation water Substances 0.000 description 9
- 239000011777 magnesium Substances 0.000 description 9
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
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- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000002329 infrared spectrum Methods 0.000 description 8
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- 229910001422 barium ion Inorganic materials 0.000 description 7
- 230000008859 change Effects 0.000 description 7
- 229910001425 magnesium ion Inorganic materials 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000003247 decreasing effect Effects 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 238000004108 freeze drying Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000007853 buffer solution Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
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- AMMWFYKTZVIRFN-UHFFFAOYSA-N sodium 3-hydroxy-4-[(1-hydroxynaphthalen-2-yl)diazenyl]-7-nitronaphthalene-1-sulfonic acid Chemical compound [Na+].C1=CC=CC2=C(O)C(N=NC3=C4C=CC(=CC4=C(C=C3O)S(O)(=O)=O)[N+]([O-])=O)=CC=C21 AMMWFYKTZVIRFN-UHFFFAOYSA-N 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- BDOYKFSQFYNPKF-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid;sodium Chemical compound [Na].[Na].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O BDOYKFSQFYNPKF-UHFFFAOYSA-N 0.000 description 1
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- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- 101001018064 Homo sapiens Lysosomal-trafficking regulator Proteins 0.000 description 1
- 102100033472 Lysosomal-trafficking regulator Human genes 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 235000010703 Modiola caroliniana Nutrition 0.000 description 1
- 244000038561 Modiola caroliniana Species 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
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- 239000013043 chemical agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
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- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1092—Polysuccinimides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
- C02F5/12—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing nitrogen
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B37/00—Methods or apparatus for cleaning boreholes or wells
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B37/00—Methods or apparatus for cleaning boreholes or wells
- E21B37/06—Methods or apparatus for cleaning boreholes or wells using chemical means for preventing or limiting, e.g. eliminating, the deposition of paraffins or like substances
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/06—Contaminated groundwater or leachate
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Mining & Mineral Resources (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Fluid Mechanics (AREA)
- Physics & Mathematics (AREA)
- Polymers & Plastics (AREA)
- Water Supply & Treatment (AREA)
- Hydrology & Water Resources (AREA)
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Abstract
The invention provides a degradable bio-based scale inhibitor, a preparation method and application thereof, wherein the molecular structure of the scale inhibitor is shown as follows:wherein n is an integer of 70 to 90. The PASP polymer is synthesized and modified, so that the scale inhibition performance of the polyaspartic acid scale inhibitor is improved, and meanwhile, the system is evaluated for Ca 2+ 、Mg 2+ 、Ba 2+ The scale inhibition effect of the scale-like substances fills up the multifunctional and universal field sites of oil fieldsBlank of the scale inhibitor and provides guidance for screening out the proper scale inhibitor on the site of the oil and gas field.
Description
Technical Field
The invention belongs to the technical field of scale inhibition in oil and gas exploitation, and particularly relates to a degradable bio-based scale inhibitor, a preparation method and application thereof.
Background
During the production of oil and gas, with the migration of formation water, when the formation water migrates along the cracks to the rock matrix, the formation water flow rate decreases and the formation water stays in the cracks of the matrix as stagnant water. When the formation water does not flow, scale forming ions and inorganic scale crystals in the formation water are in a dissolution and precipitation equilibrium state. In the process of fluid migration from the reservoir through the well bore, the thermodynamic conditions such as temperature, pressure, pH value and the like are changed drastically due to the huge temperature gradient and pressure gradient in the reservoir and the well bore, so that the initial equilibrium state of the fluid is destroyed, crystals are separated out, and scaling matters are formed. When the retained water flows from the pores in the rock to the shaft, tiny crystals in the formation water adhere to the pipe of the shaft, provide crystal nuclei for ion precipitation in the formation water, and combine other crystals in the growth process of the crystal nuclei to form a blocking shaft flow channel.
From field feedback data and relevant literature reports,the underground water of the oil-gas field contains a large amount of Ca 2+ 、Mg 2 + 、Ba 2+ And ions of inorganic salt scale are easy to form, stratum water can be extracted along with crude oil to a certain extent, when the well bottom reaches the ground, the scaling condition of fluid in the well is further aggravated due to the temperature gradient and the pressure gradient in the well, the fluid can also corrode well steel, the well blockage is aggravated, and the stable production and the yield increase of the oil and gas field are influenced very adversely. In the cooling and depressurization processes, some inorganic salts can be separated out to block the oil gas flow channel, so that the stable yield and the yield increase of the oil field are adversely affected, and the risk of under-scale corrosion is aggravated due to blockage of pipeline equipment in severe cases. The scale build-up problem of stagnant water is serious and the scale blockage problem mostly occurs in the well bore and reservoir rock in the near wellbore zone, and the selection of a proper solution is urgent. The conventional scale blocking solving method for the oil and gas field mainly comprises a physical method and a chemical method. The physical method is greatly influenced by working conditions, has complex maintenance procedures and high cost, and can not completely solve the problem of scale blockage. The chemical method has the advantages of low cost and obvious effect, and is widely used in domestic and foreign oil fields. Therefore, research on the problem of blockage of a reservoir fracture and a shaft is of great significance to oil and gas development.
The scale inhibitor is a chemical agent capable of dispersing a water-insoluble inorganic salt, and can prevent or inhibit the deposition of the insoluble inorganic salt and the formation of a precipitate. There are three general classes of scale inhibitors: inorganic salt scale inhibitors, organic monomer scale inhibitors and polymer scale inhibitors. However, at present, for oil and gas field Ca 2+ 、Mg 2+ 、Ba 2+ The research on scale inhibitors with universality of inorganic salt scale matters is not mature, and no scale inhibitor with good effects on calcium, magnesium and barium ions exists. Polyaspartic Acid (PASP) is a natural polymer scale inhibitor, has the characteristics of environmental protection, no pollution to water sources and biodegradability, and has an anti-corrosion effect, so that the PASP is also used as a synergistic agent of the corrosion inhibitor to be co-dosed. But PASP block Ca 2+ The performance is still to be further improved, and no researchers are currently available for Mg 2+ And Ba 2+ And performing relevant evaluation on the scale inhibition performance. Therefore, how to provide a method for preparing Mg 2+ And Ba 2+ The scale inhibitor with excellent scale inhibition performance of the scale-like substances becomes a problem to be solved urgently.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a degradable bio-based scale inhibitor, and a preparation method and application thereof. The PASP polymer is synthesized and modified, so that the scale inhibition performance of the polyaspartic acid scale inhibitor is improved, and meanwhile, the system is evaluated for Ca 2+ 、Mg 2+ 、Ba 2+ The scale inhibition effect of the scale-like substances fills the blank of the multifunctional and universal scale inhibitor in the oil field site and provides guidance for screening out the proper scale inhibitor in the oil field site.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a degradable bio-based scale inhibitor (GUL-PASP) having the molecular structure shown below:
where n is an integer from 70 to 90, such as 70, 75, 80, 85, or 90, etc., but is not limited to the values recited above, as are other non-recited values within the above ranges. .
The specific scale inhibitor effectively improves the scale inhibition performance of the polyaspartic acid scale inhibitor and the specific modification of the PASP polymer to Ca 2+ 、Mg 2+ 、Ba 2+ The scale-like substance has excellent scale inhibition effect, fills the blank of multifunctional and universal scale inhibitors in the oil field, and provides guidance for screening out proper scale inhibitors in the oil-gas field.
In a second aspect, the present invention provides a process for the preparation of a degradable bio-based scale inhibitor as described above, the process comprising the steps of:
and mixing polysuccinimide with water for reaction, mixing the polysuccinimide with glutamic acid for reaction, mixing the reaction solution with alcohol, and centrifuging to remove supernatant fluid to obtain the degradable bio-based scale inhibitor.
The specific preparation method can be used for efficiently preparing the scale inhibitor, and is simple and convenient to operate.
Preferably, the polysuccinimide has a number average molecular weight of 9000-12000.
Preferably, the mass ratio of polysuccinimide to glutamic acid is 1 (2-4).
Preferably, the temperature of the mixed reaction of the polysuccinimide and water is 40-70 ℃ and the time is 0.5-1.5h.
Preferably, the pH of the mixed reaction of polysuccinimide and water is 8.5-9.5.
Preferably, the temperature of the mixing reaction with glutamic acid is 40-70 ℃ and the time is 10-14h.
Preferably, the pH of the mixing reaction with glutamic acid is 6.5-7.5.
The mass ratio of polysuccinimide to glutamic acid may be 1:2, 1:2.5, 1:3, 1:3.5, 1:4, etc., the temperature of the mixed reaction of polysuccinimide and water may be 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃ or the like, the time may be 0.5h, 0.6h, 0.7h, 0.8h, 0.9h, 1h, 1.1h, 1.2h, 1.3h, 1.4h, or 1.5h, etc., the pH of the mixed reaction of polysuccinimide and water may be 8.5, 8.6, 8.7, 8.8, 8.9, 9.1, 9.2, 9.3, 9.4, 9.5, etc., the temperature of the mixed reaction of polysuccinimide and glutamic acid may be 40 ℃, 45 ℃, 55 ℃, 60 ℃, 65 ℃, or 70 ℃, etc., the time may be 10h, 10.5h, 11h, 11.5h, 12h, 12.5h, 13.7, 7.5 h, 13.7, 6.7, 7, 6.5 h, 7.7, 6, 7, 7.5, 6, 7, 6.5, or the like, and the like, but the values may not be limited to the ranges of the values recited.
In a third aspect, the invention also provides the use of a degradable bio-based scale inhibitor as described above in the preparation of an oilfield scale inhibitor.
Preferably, the degradable bio-based scale inhibitor is used for inhibiting scale of inorganic salt scales, wherein the inorganic salt scales comprise any one or a combination of at least two of calcium salt scales, magnesium salt scales and barium salt scales.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a degradable bio-based scale inhibitor, which effectively improves the scale inhibition performance of polyaspartic acid scale inhibitors and Ca by modifying PASP polymer 2+ 、Mg 2+ 、Ba 2+ The scale-like substance has excellent scale inhibition effect, fills the blank of multifunctional and universal scale inhibitors in the oil field, and provides guidance for screening out proper scale inhibitors in the oil-gas field.
Drawings
FIG. 1 is an infrared spectrum of GUL-PASP of example 1;
FIG. 2 is an infrared spectrum of GUL-PASP of example 2;
FIG. 3 is an infrared spectrum of GUL-PASP of example 3;
FIG. 4 is a graph showing the effect of GUL-PASP of examples 1-3 on the calcium scale inhibition efficiency of GUL-PASP;
FIG. 5 is an infrared spectrum of PASP;
FIG. 6 is a graph of the effect of scale inhibitor concentration on the calcium ion scale inhibition efficiency of PASP;
FIG. 7 is a graph showing the effect of heating time on the calcium ion scale inhibition efficiency of the scale inhibitor PASP;
FIG. 8 is a graph showing the effect of scale inhibitor concentration on the calcium ion scale inhibition efficiency of GUL-PASP;
FIG. 9 is a graph showing the effect of heating time on the calcium ion scale inhibition efficiency of the scale inhibitor GUL-PASP;
FIG. 10 is a graph showing the effect of scale inhibitor concentration on magnesium ion scale inhibition efficiency of GUL-PASP;
FIG. 11 is a graph showing the effect of heating time on the magnesium ion scale inhibition efficiency of the scale inhibitor GUL-PASP;
FIG. 12 is a graph showing the effect of scale inhibitor concentration on the barium ion scale inhibition efficiency of GUL-PASP;
FIG. 13 is a graph showing the effect of heating time on the barium ion scale inhibition efficiency of the scale inhibitor GUL-PASP.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
In the examples below, the number average molecular weight of the polysuccinimide is between 9000 and 12000.
Example 1
The embodiment provides a degradable biological-based scale inhibitor (GUL-PASP), which has the following structure:
wherein n has an average value of 80.
The preparation method comprises the following steps:
0.50g of Polysuccinimide (PSI) and 1.38g of glutamic acid (GUL) were weighed out separately. To beaker A, 20mL of deionized water and 0.50g of polysuccinimide were added, and stirred to form a suspension, and to beaker B, 20mL of deionized water and 1.38g of glutamic acid were added. The suspension of the beaker A is poured into a three-neck round-bottom flask with the capacity of 100mL, the three-neck round-bottom flask is heated at the water bath temperature of 40 ℃, 2mol/L sodium hydroxide is added into the round-bottom flask during the heating process, and the pH value of the round-bottom flask solution is adjusted to 9. After 1h, the temperature was raised to 60℃and the solution in the B beaker was added to the round bottom flask. After 12 hours of reaction, the heating was stopped and the pH was adjusted to 7 with a 0.1mol/L dilute hydrochloric acid solution. The reacted solution was poured into a beaker, and 300mL of absolute ethanol was added, at which time the solution became cloudy. Pouring the solution added with the absolute ethyl alcohol into a centrifuge tube, and putting the centrifuge tube into a centrifuge for centrifugal separation, wherein the rotating speed of the centrifuge is set to 6000r/min. After 5 minutes, the centrifuge tube was removed, the supernatant was decanted, and the amber oily precipitate formed at the bottom of the centrifuge tube was placed into a lyophilizer for lyophilization.
The IR spectrum of the synthesized GUL-PASP is shown in FIG. 1. GUL-PASP was analyzed at 3407cm -1 Overlapping absorption peaks of-OH and-NH-2946 cm -1 A stretching vibration absorption peak of methylene; 1645cm -1 Strong absorption peak-to-average for c=o vibration couplingThe absorption peak is stronger than that of PASP, thus indicating that the obtained product is the target product GUL-PASP.
Example 2
The embodiment provides a degradable bio-based scale inhibitor, which is prepared by the following steps:
0.50g of Polysuccinimide (PSI) and 1g of glutamic acid (GUL) were weighed out separately. To beaker A, 20mL of deionized water and 0.50g of polysuccinimide were added, and stirred to form a suspension, and to beaker B, 20mL of deionized water and 1g of glutamic acid were added. The suspension of the beaker A is poured into a three-neck round-bottom flask with the capacity of 100mL, the three-neck round-bottom flask is heated at the water bath temperature of 60 ℃, sodium hydroxide with the concentration of 2mol/L is added into the round-bottom flask during the heating process, and the pH value of the round-bottom flask solution is adjusted to 8.5. After 1.5h, the temperature was raised to 70℃and the solution in the B beaker was added to the round bottom flask. After 10 hours of reaction, the heating was stopped and the pH was adjusted to 6.5 with a 0.1mol/L dilute hydrochloric acid solution. The reacted solution was poured into a beaker, and 300mL of absolute ethanol was added, at which time the solution became cloudy. Pouring the solution added with the absolute ethyl alcohol into a centrifuge tube, and putting the centrifuge tube into a centrifuge for centrifugal separation, wherein the rotating speed of the centrifuge is set to 6000r/min. After 5 minutes, the centrifuge tube was removed, the supernatant was decanted, and the amber oily precipitate formed at the bottom of the centrifuge tube was placed into a lyophilizer for lyophilization.
The IR spectrum of the synthesized GUL-PASP is shown in FIG. 2. GUL-PASP was analyzed at 3408cm -1 Overlapping absorption peaks at-OH and-NH-; 1646cm -1 The strong absorption peak of C=O vibration coupling is stronger than that of PASP, 1399cm -1 The primary amide-CONH-C-N stretching vibration peak shows that the obtained product is the target product GUL-PASP.
Example 3
The embodiment provides a degradable bio-based scale inhibitor, which is prepared by the following steps:
0.50g of Polysuccinimide (PSI) and 2g of glutamic acid (GUL) were weighed out separately. To beaker A, 20mL of deionized water and 0.50g of polysuccinimide were added, and stirred to form a suspension, and to beaker B, 20mL of deionized water and 2g of glutamic acid were added. The suspension of the beaker A is poured into a three-neck round-bottom flask with the capacity of 100mL, the three-neck round-bottom flask is heated at the water bath temperature of 70 ℃, 2mol/L sodium hydroxide is added into the round-bottom flask during the heating process, and the pH value of the round-bottom flask solution is adjusted to 9.5. After 0.5h, the solution in the B beaker was added to the round bottom flask. After 14 hours of reaction, the heating was stopped and the pH was adjusted to 7.5 with a 0.1mol/L dilute hydrochloric acid solution. The reacted solution was poured into a beaker, and 300mL of absolute ethanol was added, at which time the solution became cloudy. Pouring the solution added with the absolute ethyl alcohol into a centrifuge tube, and putting the centrifuge tube into a centrifuge for centrifugal separation, wherein the rotating speed of the centrifuge is set to 6000r/min. After 5 minutes, the centrifuge tube was removed, the supernatant was decanted, and the amber oily precipitate formed at the bottom of the centrifuge tube was placed into a lyophilizer for lyophilization.
The IR spectrum of the synthesized GUL-PASP is shown in FIG. 3. GUL-PASP was analyzed at 3406cm -1 Overlapping absorption peaks at-OH and-NH-; 1645cm -1 The strong absorption peak of C=O vibration coupling is stronger than that of PASP, 1300cm -1 The stretching vibration peak of C-N in primary amide-CONH-shows that the obtained product is the target product GUL-PASP.
Examples 1-3 provided the target products, GUL-PASP, synthesized from Polysuccinimide (PSI) and glutamic acid (GUL) in different ratios, and compared the scale inhibition efficiencies of the target products, GUL-PASP, synthesized at three ratios, with the GUL-PASP scale inhibitor synthesized in example 2 having the smallest calcium scale inhibition efficiency (FIG. 4) and the GUL-PASP scale inhibitor synthesized in example 3 having the greatest calcium scale inhibition efficiency. Therefore, the target product GUL-PASP synthesized in example 2 was selected as the subject in the following tests, and the test was performed on Ca 2+ 、Mg 2+ 、Ba 2+ The scale inhibition performance of the invention can be better reflected.
Comparative example 1
This comparative example provides a scale inhibitor (PASP) having the following structure:
wherein n has an average value of 80.
The preparation method comprises the following steps:
first, 0.50g of Polysuccinimide (PSI) was weighed out, 20mL of deionized water and 0.50g of polysuccinimide were added to a beaker, and stirred to form a suspension. The suspension in the beaker was poured into a three-necked round-bottomed flask with a capacity of 100mL, and heated at a water bath temperature of 40℃to adjust the pH of the round-bottomed flask solution to 9 by adding sodium hydroxide with a concentration of 2mol/L to the round-bottomed flask during the heating. After 12 hours of reaction, the heating was stopped and the pH was adjusted to 7 with a 0.1mol/L dilute hydrochloric acid solution. The reacted solution was poured into a beaker, and about 300mL of absolute ethanol was added, at which time the solution became cloudy. Pouring the solution added with the absolute ethyl alcohol into a centrifuge tube, and putting the centrifuge tube into a centrifuge for centrifugal separation, wherein the rotating speed of the centrifuge is set to 6000r/min. After 5 minutes, the centrifuge tube was removed, the supernatant was decanted, and the amber oily precipitate formed at the bottom of the centrifuge tube was placed into a lyophilizer for lyophilization.
The synthesized PASP infrared spectrum is shown in FIG. 5. At 3415cm -1 A broad and strong absorption peak appears at the position, which is the superposition absorption peak of-OH and-NH-; at 1651cm -1 Is the characteristic absorption peak of N-H and C-N in the-CONH-structure; at 1590cm -1 The near absorption peak is a characteristic peak of carbonyl in the amido-carboxylic acid; at 1397cm -1 The nearby absorption peaks are formed by symmetrical stretching vibration and anti-symmetrical stretching vibration of-COO-in carboxylate, and the synthetic product is proved to be PASP.
Comparative example 2
This comparative example provides a phosphorus-free scale and corrosion inhibitor, and specific structure and preparation method refer to example 1 of CN110980971 a.
Scale inhibitor calcium ion scale formation performance test
The scale inhibition performance test of the scale inhibitor is referred to GB/T16632-2019. The scale inhibitor sample solution was formulated so that 1.00mL contained 0.500mg of the water treatment agent (on a dry basis). 250mL of the simulated water sample is added into a 500mL volumetric flask, and 10mg/mL, 30mg/mL, 50mg/mL and 100mg/mL of the scale inhibitor solution are added respectively and shaken well. The deionized water was added to the volumetric flask graduation line and shaken well.
The simulated aqueous solution with the added scale inhibition and the simulated aqueous solution without the added scale inhibition are respectively added into two clean conical flasks. The two conical flasks were immersed in a constant temperature water bath at 80℃and placed at constant temperature for 6h, 8h, 10h, 12h, 14h, respectively. The mixture was filtered dry with medium speed quantitative filter paper while hot. After the filtrate cooled, 25.00mL of the filtrate was removed and placed in a 250mL Erlenmeyer flask, water was added to about 80mL, and 5mL of 200g/L potassium hydroxide solution and about 0.1g of the calcium-carboxylic acid indicator were added. And titrating the solution by using an ethylenediamine tetraacetic acid disodium standard titration solution (0.01 mol/L) until the solution changes from purple to bright blue, and the end point is reached. The mass concentration of the calcium ions in the test solution and the blank test solution are calculated according to the following formula.
Wherein: ρ 2 Ca after the test of the test solution with the addition of the scale inhibitor 2+ The mass concentration value, mg/mL;
ρ 1 ca after blank test without scale inhibitor 2+ The mass concentration value, mg/mL;
ca after blank test of rho-non-scale inhibitor 2+ The mass concentration is the value of mg/mL.
As shown in FIG. 6, in the simulated water of the stratum, the scale inhibition rate of the PASP scale inhibitor continuously rises along with the increase of the concentration of the PASP scale inhibitor, the scale inhibition rate of the PASP scale inhibitor changes greatly along with the concentration when the concentration of the PASP scale inhibitor is lower than 50mg/L, and the scale inhibition rate of the PASP scale inhibitor is 77.78 percent and 83.33 percent respectively when the concentration of the PASP scale inhibitor is 70mg/L and 90 mg/L; as shown in FIG. 7, the scale inhibition rate of the PASP scale inhibitor was continuously decreased with the increase of the heating time, the scale inhibition rate of 90mg/L of the PASP scale inhibitor was as high as 90.74% when heating for 6 hours, the scale inhibition rate of 90mg/L of the PASP scale inhibitor was rapidly decreased to 51.87% when heating time was over 10 hours, and the scale inhibition rate of 90mg/L of the PASP scale inhibitor was increased to 14 hours.
The scale inhibition efficiency of the GUL-PASP scale inhibitor with different concentrations is shown in figure 8, in formation simulated water, the change trend of the scale inhibition rate of the GUL-PASP scale inhibitor is similar to that of SER-PASP, and the change trend of the GUL-PASP scale inhibitor is that the GUL-PASP scale inhibitor is quick and slow with the increase of the concentration of the solution. When the scale inhibitor is 70mg/L, the scale inhibition rate of GUL-PASP is 90.74 percent, and when the scale inhibitor is 90mg/L, 98.15 percent; as shown in FIG. 9, the scale inhibition rate of the GUL-PASP scale inhibitor was continuously decreased with the increase of the heating time, and the scale inhibition rate of the GUL-PASP scale inhibitor of 90mg/L was as high as 100.00% by 14 hours, and the scale inhibition rate of the GUL-PASP scale inhibitor of 90mg/L was 90.74% when heated for 6 hours.
The same test was conducted on the scale inhibitor provided in comparative example 2, and the scale inhibition rate was 78% at a higher concentration (90 mg/L). It can be found that it is significantly lower than example 1.
Scale inhibitor magnesium ion scale resistance performance test
The method for testing the performance of the scale inhibitor is the same as that of the method, the calcium ions in the simulated water are replaced by magnesium ions with the concentration of 120mg/L, an ammonia buffer solution is dripped until Congo red test paper becomes red, then 1-2mL of the ammonia buffer solution is excessive, 5 drops of chrome black T indicator are added, and the ammonia buffer solution is titrated by using disodium edetate (EDTA-2 NA) standard solution until the solution color is in a constant sky blue, and the rest steps are the same as those of the method.
The scale inhibition efficiency of the GUL-PASP scale inhibitor with different concentrations is shown in figure 10, and the change trend of the scale inhibition rate of the GUL-PASP scale inhibitor in stratum simulated water shows a trend of going fast and slow. When the scale inhibitor is 70mg/L, the scale inhibition rate of GUL-PASP is 89.61%, and when the scale inhibitor is 90mg/L, the scale inhibition rate is 97.98%; as shown in FIG. 11, the scale inhibition rate of the GUL-PASP scale inhibitor was continuously decreased with the increase of the heating time, and the scale inhibition rate of the GUL-PASP scale inhibitor of 90mg/L was as high as 100.00% by 14 hours, and the scale inhibition rate of the GUL-PASP scale inhibitor of 90mg/L was 90.32% when heated for 6 hours.
In comparative example 1, the change of the scale inhibition rate of PASP scale inhibitors with different concentrations in formation simulated water is similar to that of GUL-PASP scale inhibitor, and the change of the scale inhibition rate of PASP scale inhibitors in formation simulated water is in a trend of first quick and then slow. When the scale inhibitor is 70mg/L, the scale inhibition rate of PASP is 73.19 percent, and when the scale inhibitor is 90mg/L, 81.03 percent; the PASP scale inhibition rate is continuously reduced along with the increase of the heating time, the 90mg/L PASP scale inhibition rate is 89.37 percent when the heating is carried out for 6 hours, and the 90mg/L PASP scale inhibition rate is 58.99 percent when the heating is carried out for 14 hours.
Comparing the data, the degradable biological-based scale inhibitor (GUL-PASP) provided by the invention has higher magnesium ion scale inhibition performance than PASP scale inhibitor.
Through comparison test, in comparative example 2, when the concentration of the scale inhibitor is 70mg/L, the scale inhibition rate is 75.47%, and when the concentration of the scale inhibitor is 90mg/L, the scale inhibition rate is 84.68%; the scale inhibition rate of the scale inhibitor is continuously reduced along with the increase of the heating time, the scale inhibition rate of the scale inhibitor with the concentration of 90mg/L is 88.65 percent when the scale inhibitor is heated for 6 hours, and the scale inhibition rate of the scale inhibitor with the concentration of 90mg/L is 62.34 percent when the scale inhibitor is heated for 14 hours.
Comparing the data, the degradable biological-based scale inhibitor (GUL-PASP) provided by the invention has higher magnesium ion scale inhibition performance than pure PASP and the scale inhibitor in the prior art.
Scale inhibitor barium ion scale resistance performance test
The performance test of the scale inhibitor is the same as that of the scale inhibitor, the calcium ions in the simulated water are replaced by barium ions with the concentration of 20mg/L, the equivalent EDTA standard solution (skip amount) is added into the simulated formation water, 5 drops of chrome black T indicator is added, and ZnSO is used 4 And (3) back-titration of the standard solution until the color of the solution is changed from blue to mauve, wherein the rest steps are the same.
The scale inhibition efficiency of the GUL-PASP scale inhibitor with different concentrations is shown in figure 12, and the change trend of the scale inhibition rate of the GUL-PASP scale inhibitor in stratum simulated water still shows a trend of going fast and slow. When the scale inhibitor is 70mg/L, the scale inhibition rate of GUL-PASP is 90.27 percent, and when the scale inhibitor is 90mg/L, 99.18 percent; as shown in FIG. 13, the scale inhibition rate of the GUL-PASP scale inhibitor was continuously decreased with the increase of the heating time, and the scale inhibition rate of the GUL-PASP scale inhibitor of 90mg/L was as high as 99.80% by 14 hours, and the scale inhibition rate of the GUL-PASP scale inhibitor of 90mg/L was 92.41% when heated for 6 hours.
The change of the scale inhibition rate of PASP scale inhibitors with different concentrations in stratum simulated water is similar to that of GUL-PASP scale inhibitors, and the PASP scale inhibitors all show a trend of being quick and slow. When the concentration of the scale inhibitor is 70mg/L, the scale inhibition rate of PASP is 68.94 percent, and when the concentration of the scale inhibitor is 90mg/L, 83.12 percent; the PASP scale inhibition rate is continuously reduced along with the increase of the heating time, the PASP scale inhibition rate of 90mg/L is 87.85% when the heating is carried out for 6 hours, and the PASP scale inhibition rate of 90mg/L is 69.31% when the heating is carried out for 14 hours.
Comparing the data, the degradable biological-based scale inhibitor (GUL-PASP) provided by the invention has higher barium ion scale inhibition performance than PASP scale inhibitor.
Through tests, the scale inhibitor in the comparative example 2 has a scale inhibition rate of 70.32% when the concentration of the scale inhibitor is 70mg/L, and has a scale inhibition rate of 85.64% when the concentration of the scale inhibitor is 90 mg/L; the scale inhibition rate of the scale inhibitor is continuously reduced along with the increase of the heating time, the scale inhibition rate of the scale inhibitor with the concentration of 90mg/L is 90.21 percent when the scale inhibitor is heated for 6 hours, and the scale inhibition rate of the scale inhibitor with the concentration of 90mg/L is 75.87 percent when the scale inhibitor is heated for 14 hours.
Comparing the data, the degradable biological-based scale inhibitor (GUL-PASP) provided by the invention has higher barium ion scale inhibition performance than pure PASP and the scale inhibitor in the prior art.
The applicant states that the present invention is illustrated by the above examples as well as the preparation method and application thereof, but the present invention is not limited to the above examples, i.e. it is not meant that the present invention must be practiced in dependence upon the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Claims (10)
1. A degradable bio-based scale inhibitor, characterized in that the molecular structure of the scale inhibitor is as follows:
wherein n is an integer of 70 to 90.
2. A method of preparing a degradable bio-based scale inhibitor according to claim 1, comprising the steps of:
and mixing polysuccinimide with water for reaction, mixing the polysuccinimide with glutamic acid for reaction, mixing the reaction solution with alcohol, and centrifuging to remove supernatant fluid to obtain the degradable bio-based scale inhibitor.
3. The method of claim 2, wherein the polysuccinimide has a number average molecular weight of 9000-12000.
4. A method according to claim 2 or 3, wherein the mass ratio of polysuccinimide to glutamic acid is 1 (2-4).
5. The process according to any one of claims 2 to 4, wherein the polysuccinimide is mixed with water at a temperature of 40 to 70 ℃ for a time of 0.5 to 1.5 hours.
6. The process according to any one of claims 2 to 5, wherein the polysuccinimide is mixed with water at a pH of 8.5 to 9.5.
7. The method according to any one of claims 2 to 6, wherein the temperature of the mixing reaction with glutamic acid is 40 to 70 ℃ for 10 to 14 hours.
8. The method according to any one of claims 2 to 7, wherein the pH of the mixing reaction with glutamic acid is 6.5 to 7.5.
9. Use of a degradable bio-based scale inhibitor according to claim 1 in the preparation of an oilfield scale inhibitor.
10. The use according to claim 9, wherein the degradable bio-based scale inhibitor is used to inhibit scale of inorganic salt scale including any one or a combination of at least two of calcium salt scale, magnesium salt scale or barium salt scale.
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