CN114605979A - Calcium carbonate scale inhibitor for oil field and preparation method thereof - Google Patents
Calcium carbonate scale inhibitor for oil field and preparation method thereof Download PDFInfo
- Publication number
- CN114605979A CN114605979A CN202210107610.6A CN202210107610A CN114605979A CN 114605979 A CN114605979 A CN 114605979A CN 202210107610 A CN202210107610 A CN 202210107610A CN 114605979 A CN114605979 A CN 114605979A
- Authority
- CN
- China
- Prior art keywords
- calcium carbonate
- scale inhibitor
- scale
- temperature
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 100
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 52
- 239000002455 scale inhibitor Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 108010064470 polyaspartate Proteins 0.000 claims abstract description 61
- 229920000805 Polyaspartic acid Polymers 0.000 claims abstract description 60
- 239000000243 solution Substances 0.000 claims abstract description 52
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910001868 water Inorganic materials 0.000 claims abstract description 27
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 229920001577 copolymer Polymers 0.000 claims abstract description 11
- 239000002244 precipitate Substances 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000005485 electric heating Methods 0.000 claims abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 5
- 230000007935 neutral effect Effects 0.000 claims abstract description 5
- 239000012266 salt solution Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 4
- ATLMFJTZZPOKLC-UHFFFAOYSA-N C70 fullerene Chemical compound C12=C(C3=C4C5=C67)C8=C9C%10=C%11C%12=C%13C(C%14=C%15C%16=%17)=C%18C%19=C%20C%21=C%22C%23=C%24C%21=C%21C(C=%25%26)=C%20C%18=C%12C%26=C%10C8=C4C=%25C%21=C5C%24=C6C(C4=C56)=C%23C5=C5C%22=C%19C%14=C5C=%17C6=C5C6=C4C7=C3C1=C6C1=C5C%16=C3C%15=C%13C%11=C4C9=C2C1=C34 ATLMFJTZZPOKLC-UHFFFAOYSA-N 0.000 claims description 2
- 230000005764 inhibitory process Effects 0.000 abstract description 31
- 239000011575 calcium Substances 0.000 abstract description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052791 calcium Inorganic materials 0.000 abstract description 5
- 235000010216 calcium carbonate Nutrition 0.000 description 37
- 238000012360 testing method Methods 0.000 description 19
- 239000003921 oil Substances 0.000 description 15
- 239000013078 crystal Substances 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 11
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 9
- 230000002265 prevention Effects 0.000 description 9
- 239000000523 sample Substances 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 8
- 238000005259 measurement Methods 0.000 description 7
- 230000002776 aggregation Effects 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 238000005054 agglomeration Methods 0.000 description 5
- -1 and the solubility Substances 0.000 description 5
- 229910003472 fullerene Inorganic materials 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 230000007246 mechanism Effects 0.000 description 5
- 239000013081 microcrystal Substances 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- 239000012488 sample solution Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000012490 blank solution Substances 0.000 description 4
- 229910001424 calcium ion Inorganic materials 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Inorganic materials [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000007667 floating Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 229940009098 aspartate Drugs 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000013043 chemical agent Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002332 oil field water Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 230000003449 preventive effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012719 thermal polymerization 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
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000668 effect on calcium Effects 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 229920001308 poly(aminoacid) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
- C09K8/528—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning inorganic depositions, e.g. sulfates or carbonates
-
- 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/10—Alpha-amino-carboxylic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of a calcium carbonate scale inhibitor for an oil field, which comprises the following steps: adding a certain amount of water, maleic anhydride and citric acid into a reactor, placing the reactor on an electric heating sleeve to control the temperature and heat, dropwise adding ammonia water at a certain temperature, continuously heating, reacting for a period of time to obtain a copolymer, cooling, hydrolyzing the PSI copolymer by using an alkali solution with a certain concentration to obtain a reddish brown clarified liquid, namely a salt solution of the polyaspartic acid copolymer, adjusting the solution to be neutral by using dilute hydrochloric acid, adding ethanol, mixing to form a reddish brown precipitate, filtering the precipitate, and drying to obtain the polyaspartic acid copolymer. The invention also evaluates the performance of the polyaspartic acid scale inhibitor, measures the scale inhibition rate of the calcium scale, and respectively measures the influence of temperature, pH value and concentration on the scale inhibition rate of the calcium scale.
Description
Technical Field
The invention relates to the technical field of scale inhibitors, in particular to a calcium carbonate scale inhibitor for oil fields and a preparation method thereof.
Background
Scaling is obviously harmful, and oil and gas production is reduced, water injection pressure is increased, and underground and ground equipment even stops production and is scrapped. The economic loss of oil and gas wells and surface equipment due to fouling is reported to be $ 10 billion annually in the united states. Carbonate scale is the most common scale in oil and gas field production, but is easy to remove by acidification and has relatively small harm, while sulfate scale is difficult to remove by a common method and has great harm. The composition and the descaling mechanism of the anti-scaling agent are deeply researched by combining the further introduction of the reasons and the processes of oil field scaling and the development and the performance of the anti-scaling agent emphasized by the related information at home and abroad in recent years through the mechanism analysis and the related discussion of the preparation and the descaling of the anti-scaling agent.
It is reported that at present, in foreign countries, polyaspartate, a readily biodegradable scale inhibitor, has been developed, and this product has been initially tested on site in the production of oil in the north sea field and in the european coal mining. The test results show that the aspartate polymer antiscalant is used for preventing CaCO3And BaSO4The fouling molecular weight is most effective between 3000Mw and 4000Mw, and the molecular weight is most suitable for CaSO when the molecular weight is between 1000Mw and 2000Mw4And (4) preventing scale. Meanwhile, the aspartate polymer also has the anticorrosion effect, and is especially suitable for oil field CO2The corrosion prevention effect in a corrosive environment is more prominent. It has also been reported that various long-acting scale inhibitors have been developed abroad in order to extend the treatment period of validity of the scale inhibitor, such as a long-acting scale inhibitor recently developed by Mobil oil company for preventing oil well fouling. The scale inhibitor consists of a scale inhibitor, polyvalent metal ions and a thermosensitive pH increasing agent, and can slowly release effective components.
Polyaspartic Acid (PASP) belongs to a class of polyamino acids. The peptide bond on the structural main chain of the polyaspartic acid is easy to be broken by the action of microorganisms, fungi and the like, and the final degradation products are ammonia, carbon dioxide and water which are harmless to the environment. Polyaspartic acid has wide application. Can find its application in the fields of water treatment, medicine, agriculture and daily chemicals. As a water treatment agent, it has the main functions of scale inhibition and/or dispersion and corrosion inhibition. The scale inhibitor is particularly suitable for inhibiting the formation of calcium carbonate scale, calcium sulfate scale, barium sulfate scale and calcium phosphate scale in cooling water, boiler water and reverse osmosis treatment.
According to the invention, through the analysis of the composition and the property of the oil field water, the mechanism of formation of the oil field water scale and the classification research of the scale inhibitor, the polyaspartic acid as the scale inhibitor is found to have good effect, is biodegradable and hardly has pollution caused by emission. The polyaspartic acid is synthesized by using maleic anhydride, citric acid and ammonia water as raw materials, and the solubility, solid content and anti-scaling rate of the polyaspartic acid are measured, and the influence of the concentration, pH value and temperature of a medicine on the anti-scaling rate of the polyaspartic acid is researched and discussed.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a preparation method of a calcium carbonate scale inhibitor for an oil field.
The technical scheme of the invention is as follows:
a preparation method of a calcium carbonate scale inhibitor for oil fields comprises the following steps: adding a certain amount of water, Maleic Anhydride (MA) and citric acid into a reactor, placing the reactor on an electric heating sleeve to control the temperature and heat, dropwise adding ammonia water at a certain temperature, continuously heating, reacting for a period of time to obtain a copolymer, cooling, hydrolyzing the PSI copolymer by using an alkali solution with a certain concentration to obtain a reddish brown clarified liquid, namely a salt solution of the polyaspartic acid copolymer, adjusting the solution to be neutral by using dilute hydrochloric acid, adding ethanol for mixing to form a reddish brown precipitate, filtering the precipitate, and drying to obtain the polyaspartic acid copolymer, namely the calcium carbonate antiscaling agent for the oil field.
Preferably, in the preparation process, the proportion of each raw material is as follows: n (maleic anhydride)/n (ammonia)/n (citric acid) ═ 1/2.34/0.1.
Preferably, in the preparation process, the reaction temperature is 180 ℃.
Preferably, in the preparation process, the reaction time is 10 min.
Preferably, the mass concentration of the anti-scaling agent is 1.0-2.0% when in use.
Preferably, the temperature of the anti-scaling agent is 40-80 ℃ when in use.
Preferably, the pH of the anti-scaling agent is 7.8-8.2 at the time of use.
The above optimal preparation conditions were obtained by analyzing the preparation method using orthogonal experiments
Factors affecting the synthesis of polyaspartic acid are the ratio of ammonia to maleic anhydride, the ratio of maleic anhydride to citric acid, the thermal polymerization time and the thermal polymerization temperature. It was determined to be the test factor for this test and noted A, B, C and D, respectively, and a four-factor orthogonal test was performed, each factor being at three levels, the factor levels being shown in Table 1.
Table 1: factor level meter
The experiment has 4 3 level factors, L9(34) or L27(313) can be selected, and an L9(34) orthogonal table is preferably selected because the experiment only considers the influence effect of four factors on the scale prevention rate and does not consider the interaction among the factors. If the interaction is to be examined, L27(313) should be chosen.
Table 2: results of orthogonal test analysis
As can be seen from Table 2, the optimum process conditions for producing polyaspartic acid are: n (maleic anhydride)/n (ammonia)/n (citric acid) ═ 1/2.34/0.1; the reaction temperature is 180 ℃; the reaction time was 10 min. The influence of the heat polymerization temperature is the largest and the influence of the heat polymerization time is the smallest.
The reaction equation of the preparation method is as follows:
analysis of calcium carbonate Scale inhibition mechanism by Scale inhibitor
The mechanism of scale inhibition by polyaspartic acid is mainly agglomeration and subsequent dispersion. The scale layer forming calcium carbonate, calcium sulfate and other small crystal particles need to collide constantly in water solution and are arranged in strict lattice order to grow from crystal nucleus into large crystal, and polyaspartic acid and other anionic scale inhibitor may be dissociated into negative ion in water solution. When the negative ions collide with calcium carbonate microcrystals in the aqueous solution, physical adsorption and chemical adsorption processes are firstly carried out, and an electric double layer is formed on the crystal surface as a result of adsorption, so that the microcrystals can be charged with the same charge when one polymer negative ion and two or more calcium carbonates are adsorbed. There is electrostatic repulsion between them, thus hindering the collision between them and the formation of large crystals, and also hindering the collision between them and the metal heat transfer surface and the formation of scale layer, which is the condensation of anionic antiscalants. The agglomeration causes the aggregation of the microcrystals in the aqueous solution to some extent, but the agglomeration does not so far, and when the adsorption product encounters another organic molecule or the adsorption product diffuses to a region where the concentration of the organic molecule is relatively high, the adsorbed particles are handed over to another molecule, and finally, an average dispersion state is presented, that is, a dispersion state after the agglomeration of the crystal particles by the negative ion of the organic molecule, and the agglomeration and the subsequent dispersion cause the microcrystals having a potential for scale formation to be stably suspended in the water, that is, the collision of the crystal particles with the metal surface is hindered, and thus, the growth of the scale layer is also inhibited.
Furthermore, this action correspondingly reduces the number of crystal nuclei required for scale formation (in a supersaturated solution, crystallization and crystal growth hardly occur if no crystal nuclei are present). Therefore, more calcium carbonate can be contained in the water without being precipitated out of the water, so that the crystallization speed of the calcium carbonate is reduced, the crystals are kept in a very small particle state, the contact surface of the crystals and the water is enlarged, and the dissolution performance of the crystals is improved.
Further preferably, the calcium carbonate scale inhibitor is added with hydroxylated fullerene when in use.
More preferably, the hydroxylated fullerene is one or a combination of two of a fullerene C60 hydroxylated derivative and a fullerene C70 hydroxylated derivative.
In the hydroxylated fullerene, the number of hydroxylations is 20-32.
Further preferably, the addition amount of the hydroxylated fullerene is 0.1-0.25% of the mass of the calcium carbonate scale inhibitor.
The invention has the advantages that:
the preparation method of the calcium carbonate scale inhibitor for the oil field comprises the following steps: adding a certain amount of water, Maleic Anhydride (MA) and citric acid into a reactor, placing the reactor on an electric heating sleeve, controlling the temperature, heating, dropwise adding ammonia water at a certain temperature, continuously heating, reacting for a period of time to obtain a copolymer, cooling, hydrolyzing the PSI copolymer by using an alkali solution with a certain concentration to obtain a reddish brown clarified liquid, namely a salt solution of the polyaspartic acid copolymer, adjusting the solution to be neutral by using dilute hydrochloric acid, adding ethanol, mixing to form a reddish brown precipitate, filtering the precipitate, and drying to obtain the polyaspartic acid copolymer.
1. The polyaspartic acid is synthesized by taking maleic anhydride, citric acid and ammonia water as raw materials, and the optimal synthesis process conditions are obtained through an orthogonal test: n (maleic anhydride)/n (ammonia)/n (citric acid) ═ 1/2.34/0.1; the reaction temperature is 180 ℃; the reaction time was 10 min.
2. When the mass concentration of the polyaspartic acid scale inhibitor is 1%, the liquid is clear and transparent, no floating object exists on the liquid surface, no sediment exists at the bottom of a beaker, and the polyaspartic acid is dissolved in water, and the solid content of the polyaspartic acid is 51.5-52.5% by measurement.
3. CaCO formed by polyaspartic acid scale agent on pure oil field sewage3The calcium carbonate anti-scaling agent has an excellent anti-scaling effect, the addition of an anti-scaling agent solution is in a small range of 2-6 mg/L, the calcium carbonate anti-scaling rate is increased along with the increase of the addition of the anti-scaling agent, and when the addition of the anti-scaling agent is 6mg/L, the anti-scaling rate can reach over 90 percent.
4. As the temperature of the system is increased, the calcium carbonate scale prevention rate of the polyaspartic acid scale inhibitor is reduced. When the temperature is in the range of 40-80 ℃, the scale prevention rate is over 90 percent, which indicates that the polyaspartic acid has better temperature resistance.
5. The pH value of the system also has certain influence on the anti-scaling rate, when the pH value is increased, the anti-scaling rate of the polyaspartic acid is increased firstly and then reduced, and when the pH value is 8, the anti-scaling rate of the polyaspartic acid reaches the maximum.
6. The fullerene has good capability of absorbing free radicals, which is beneficial to gathering microcrystals in aqueous solution around the fullerene, and the special spherical structure of the fullerene enables the contact surface between different fullerene and fullerene spherical molecules to be smaller, thus being beneficial to further dispersion of crystal particles, and having better anti-scaling effect on calcium carbonate.
Drawings
FIG. 1: the influence of temperature on the scale prevention rate.
FIG. 2: the influence of pH value on the scale prevention rate is shown.
Detailed Description
Example 1
A preparation method of a calcium carbonate scale inhibitor for oil fields comprises the following steps: adding a certain amount of water, Maleic Anhydride (MA) and citric acid into a reactor, placing the reactor on an electric heating sleeve, controlling the temperature, heating, dropwise adding ammonia water at a certain temperature, continuously heating, reacting for a period of time to obtain a copolymer, cooling, hydrolyzing the PSI copolymer by using an alkali solution with a certain concentration to obtain a reddish brown clarified liquid, namely a salt solution of the polyaspartic acid copolymer, adjusting the solution to be neutral by using dilute hydrochloric acid, adding ethanol, mixing to form a reddish brown precipitate, filtering the precipitate, and drying to obtain the polyaspartic acid copolymer.
n (maleic anhydride)/n (ammonia)/n (citric acid) ═ 1/2.34/0.1; the reaction temperature is 180 ℃; the reaction time was 10 min.
The properties of the polyaspartic acid copolymer prepared were measured as follows.
Test example 1 determination of Water solubility of polyaspartic acid
The specific test method comprises the following steps:
preparation of sample solution
Firstly, 1.00 +/-0.01 g of polyaspartic acid is taken in a 250ml glass beaker;
② adding 99.00 +/-0.05 g of distilled water into the beaker;
placing a magnetic stirring rotor in the beaker and then placing the beaker on a magnetic stirrer;
and fourthly, turning on a power supply of the magnetic stirrer, and setting the rotating speed to be 300r/min for stirring for 5 min.
Method for determining water solubility
Firstly, starting a power supply of a constant-temperature water bath, and setting the water temperature to be 25 ℃;
placing a 250mL glass beaker containing the sample solution in a constant-temperature water bath, and keeping the temperature for 10 min;
taking the beaker out of the constant-temperature water bath, observing under natural light, judging the beaker to be dissolved if the liquid in the beaker is clear and transparent, no floating object exists on the liquid surface and no sediment exists at the bottom of the beaker, and judging the beaker not to be dissolved if the liquid is clear and transparent.
And (3) testing results:
and observing under natural light, wherein the liquid in the beaker is clear and transparent, no floating object exists on the liquid surface, no sediment exists at the bottom of the beaker, and the sample is judged to be dissolved.
Test example 2 determination of solid content of polyaspartic acid
Measurement procedure
Firstly, a power supply of a constant-temperature drying oven is connected, the temperature of the constant-temperature drying oven is set to be 120 ℃, and the constant temperature is kept for 1 hour.
② the beaker is placed in a constant temperature drying box and dried for 2 hours at the temperature of 120 ℃.
And thirdly, taking the beaker out of the constant-temperature drying box, and cooling the beaker in a dryer for 30 min.
Fourthly, weighing the mass of the dry beaker on a balance, accurately obtaining 0.0001g, and considering the mass as m1。
Fifthly, adding 9g to 11g of uniformly mixed sample into the beaker, weighing the sample on a balance until the mass reaches 0.0001g, and determining the mass as m2And drying the mixture in a constant-temperature drying box at 120 ℃ for 8 hours.
Sixthly, moving the dried sample into a dryer, and cooling for 30min to room temperature.
Seventhly, weighing the mass on a balance to be accurate to 0.0001g, and considering the mass as m3。
2.2.4.2 method for calculating result
The solid content mass percent is calculated according to the following formula:
in the formula:
s-solid content of sample,%;
m1-mass of the drying beaker, g;
m2-mass of sample plus beaker before drying, g;
m3-mass of dried sample plus beaker, g.
And (3) testing results:
m1＝73.5435g；m2＝83.4455g；m3＝78.3032g
test example 3 measurement of calcium carbonate scale inhibition ratio of scale inhibitor
Preparation of sample solution
2mol/L aqueous sodium hydroxide solution: 8g of sodium hydroxide was dissolved in 100mL of distilled water. The product is stored in a polyethylene bottle to avoid the pollution of carbon dioxide in the air.
Disodium ethylenediaminetetraacetic acid (EDTA): the mixture was previously prepared with distilled water to give an aqueous solution having a concentration of 0.01 mol/L.
Calcium indicator: 1.0g of calcium carboxylic acid and 50g of sodium chloride which has been dried at 105 ℃ are ground in a mortar, passed through a standard sieve of 40 to 50 mesh and stored in a brown ground bottle.
Solution A: respectively weighing 2.89 +/-0.01 g of anhydrous CaCl20.62. + -. 0.01g of MgCl at a concentration of 1%2·6H2Adding the O aqueous solution into a 200mL beaker, adding distilled water, transferring into a 1000mL volumetric flask, uniformly mixing, and fixing the volume.
Solution B: weighing 1.31 + -0.01 g NaCl and 3.20 + -0.01 g NaHCO respectively3、0.20±0.01gNa2CO30.63. + -. 0.01g of 1% Na2SO4Adding distilled water into a 200mL beaker, transferring the water solution into a 1000mL volumetric flask, uniformly mixing, and fixing the volume.
Solution C: weighing 0.50 +/-001 g of the scale inhibitor sample in a 100mL beaker, adding distilled water, transferring the sample into a 100mL volumetric flask, adding distilled water to a scale mark, and shaking uniformly to prepare a 0.5% corrosion and scale inhibitor solution.
Solution D: 10mL of the solution A was pipetted into a 250mL conical flask with a stopper and mixed well with 190mL of distilled water.
Measurement procedure
(1) Transferring 10mL of the solution A into a conical flask with a plug and a capacity of 250mL by using a pipette, adding 190mL of the solution B, tightly covering the bottle plug, and fully shaking up to obtain a blank solution.
(2) Transferring 10mL of the solution A into a conical flask with a plug and a capacity of 250mL by using a pipette, adding 0.8mL of the solution C, fully shaking up, adding 190mL of the solution B, tightly covering the bottle plug, and shaking up to obtain a dosing solution.
(3) And (3) putting the conical flask into an electric heating air blowing drying oven with the temperature of 70 +/-1 ℃ for keeping the temperature for 10 hours, taking out the conical flask, and cooling to room temperature.
(4) The solutions were filtered separately through medium speed filter paper.
(5) Respectively taking 10mL of the filtered blank solution and the medicated solution by using a pipette, adjusting the pH value to 12-13 by using a 2mol/L NaOH aqueous solution, adding a little calcium reagent, titrating to the end point by using an EDTA solution (the solution is changed from red to basket color), and recording the consumption volume of the EDTA solution. The volume of EDTA solution consumed by the dosing solution was recorded as V1The volume of EDTA solution consumed in the blank solution is recorded as V0。
(6) 10mL of the D solution was collected, titrated with EDTA to the end point, and the consumption of the EDTA solution was recorded as V.
(7) The calcium carbonate scale inhibition ratio of polyaspartic acid was calculated using the following formula:
scale inhibition ratio EfCalculating the formula:
in the formula:
Ef-fouling prevention rate,%;
V1-the dosing solution consumes the volume of EDTA in mL;
V0-the blank solution consumes the volume of EDTA in mL;
V-D the volume of EDTA dissolved in mL.
And (3) testing results:
V＝1.15ml；V0＝0.05ml；V1＝0.78ml。
from equation 1:
test example 4 measurement of calcium carbonate Scale inhibition ratio of Scale inhibitor at different concentrations
Because the scale prevention rate of many scale inhibitors does not increase with the increase of the concentration of the chemical agent, and even on the contrary, sometimes the scale prevention effect is rather reduced because the concentration of the chemical agent is too large. This peculiar effect of the copolymer is known as the "solution-limiting effect". The polyaspartic acid scale inhibitor synthesized in the experiment is respectively prepared into scale inhibitor solutions with mass concentrations of 0.5%, 1.0% and 1.5%, other conditions are unchanged, and the respective scale inhibition rates are respectively determined by applying a method for determining the calcium carbonate scale inhibition rate of polyaspartic acid.
And (3) testing results:
table 3: anti-scaling rate of anti-scaling agent with different concentrations
As can be seen from Table 3, the amount of the solution of the scale inhibitor is in a small range of 2-6 mg/L, the calcium carbonate scale inhibition rate of the polyaspartic acid increases with the increase of the amount of the scale inhibitor, and the scale inhibition efficiency is better.
Test example 5 measurement of calcium carbonate scale preventive ratio of scale preventive at different temperatures
The temperature can change the solubility of the salt easy to scale, and CaCO is added along with the increase of the temperature3The solubility of (b) is lowered, and the precipitation is gradual to form scale. At the same time, Ca (HCO) is also generated by the increase of temperature3)2Decomposition to produce CaCO3While scaling, the reaction is endothermic, with temperature increase and equilibrium shift to the right, favoring CaCO3Thereby precipitating Ca in the solution2+The concentration decreases. Therefore, the temperature is adjusted to 40-80 ℃ in the experimentIn the range, the addition of the scale inhibitor is 6mg/L, the solution A, the solution B and the solution C are respectively prepared according to the preparation method of the sample solution, and the scale inhibition rate of the polyaspartic acid at different temperatures is respectively measured by applying a calcium carbonate scale inhibition rate measuring method of the polyaspartic acid.
And (3) testing results:
because the temperature has great influence on the solubility of the scaling substances in water and the ion balance in water, the temperature is adjusted to be within the range of 40-80 ℃ in an experiment, the addition amount of the scale inhibitor is 6mg/L (namely the mass concentration of the scale inhibitor solution is 1.5%), the calcium carbonate scale inhibition rate of polyaspartic acid is measured by using a method for measuring the calcium carbonate scale inhibition rate of polyaspartic acid, the obtained experiment results are shown in Table 4, and the calcium carbonate scale inhibition rate of polyaspartic acid at different temperatures is shown in figure 1.
Table 4: scale control rate of scale inhibitor at different temperatures
As can be seen from FIG. 1, the calcium carbonate scale inhibition ratio of polyaspartic acid decreased with an increase in temperature. When the temperature is in the range of 40-80 ℃, the scale prevention rate is over 90 percent, which indicates that the polyaspartic acid has better temperature resistance. The temperature influence is mainly to change the solubility of the easily scaling salt, and as the temperature rises, CaCO3The solubility of (b) is lowered, and the precipitation is gradual to form scale. At the same time, the increase in temperature also causes Ca (HCO)3)2Decomposition to produce CaCO3While scaling, the reaction is endothermic, with temperature increase, equilibrium shift to the right, favoring CaCO3Thereby precipitating Ca in the solution2+The concentration decreases. The temperature also disrupts the ionic equilibrium of the system and the increase in temperature causes HCO3-Decomposing and increasing CO3 in water2-Content, causing disruption of the ionic balance. The overall balance is affected by temperature and compositional changes, with the greater the degree of damage, the greater the tendency for scale deposition to occur.
Test example 6 measurement of calcium carbonate anti-scaling Rate of polyaspartic acid at different pH values
Because the pH value greatly influences the dissociation degree and the chelating performance of carboxyl in a chemical structure of the polyaspartic acid, in an experiment, the solution A, the solution B and the solution C are respectively prepared according to the preparation method of the sample solution when the pH value is within 7-12 and the addition amount of the scale inhibitor is 6mg/L, and the scale inhibition rate of the polyaspartic acid at different pH values is respectively determined by applying the calcium carbonate scale inhibition rate determination method of the polyaspartic acid.
Test results
As the pH value greatly influences the dissociation degree and the chelating property of the carboxyl in the chemical structure of the polyaspartic acid, in the experiment, the pH value is in the range of 7-12, the addition amount of the scale inhibitor is 6mg/L, the calcium carbonate scale inhibition rate of the polyaspartic acid is measured by using the method for measuring the calcium carbonate scale inhibition rate of the polyaspartic acid, the scale inhibition rates of the polyaspartic acid at different pH values are respectively measured, the obtained experiment results are listed in Table 5, and the calcium carbonate scale inhibition rates of the polyaspartic acid at different pH values are shown in figure 2.
As can be seen from fig. 2, the pH value of the system also has a certain influence on the scale inhibition rate, and when the pH value is increased, the scale inhibition rate of polyaspartic acid is increased and then decreased, and when the pH value is 8, the scale inhibition rate of polyaspartic acid is maximized. In the low pH range, the scale inhibition rate of polyaspartic acid increases with increasing pH, and when pH is >8, the calcium ion concentration at the time of scale formation decreases with increasing pH. This is because the saturation solubility of silicon ions increases with increasing pH, but at higher pH, the precipitation tendency of calcium and magnesium ions in the solution increases, and the precipitates of calcium and magnesium ions become the core of silica scale deposition, promoting the formation of silica scale, reducing the concentration of silicon ions during the formation of scale, and simultaneously reducing the calcium ions.
Test example 8 influence of the addition of hydroxylated fullerene on the calcium carbonate scale inhibition ratio of polyaspartic acid.
Table 5: after the hydroxylated fullerene is added, the anti-scaling rate of the anti-scaling agent is controlled under the condition of 40 ℃ and pH 8;
as can be seen from Table 5, the scale control effect of the scale inhibitor is significantly improved after the addition of the hydroxylated fullerene.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (9)
1. A preparation method of a calcium carbonate scale inhibitor for oil fields is characterized by comprising the following steps: adding a certain amount of water, maleic anhydride and citric acid into a reactor, placing the reactor on an electric heating sleeve to control the temperature and heat, dropwise adding ammonia water at a certain temperature, continuously heating, reacting for a period of time to obtain a copolymer, cooling, hydrolyzing the PSI copolymer by using an alkali solution with a certain concentration to obtain a reddish brown clarified liquid, namely a salt solution of the polyaspartic acid copolymer, adjusting the solution to be neutral by using dilute hydrochloric acid, adding ethanol, mixing to form a reddish brown precipitate, filtering the precipitate, and drying to obtain the polyaspartic acid copolymer.
2. The method for preparing calcium carbonate scale inhibitor for oil field according to claim 1, wherein the raw materials are in the following proportion: n (maleic anhydride)/n (ammonia)/n (citric acid) ═ 1/2.34/0.1.
3. The method of claim 1, wherein the reaction temperature is 180 ℃.
4. The method of claim 1, wherein the reaction time is 10 min.
5. The calcium carbonate scale inhibitor for oil field prepared by the method of any one of claims 1 to 4.
6. The calcium carbonate scale inhibitor for oil field use according to claim 5, wherein the scale inhibitor has a mass concentration of 1.0% to 2.0% in use.
7. The calcium carbonate scale inhibitor for oil field use according to claim 5, wherein the temperature of the scale inhibitor is 40-80 ℃ in use; the pH value is 7.8-8.2.
8. The calcium carbonate scale inhibitor for oil field use according to claim 5, wherein the calcium carbonate scale inhibitor is added to the hydroxylated fullerene at the time of use.
9. The calcium carbonate scale control agent for oil field as claimed in claim 8, wherein the hydroxylated fullerene is any one or combination of fullerene C60 hydroxylated derivative and fullerene C70 hydroxylated derivative.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210107610.6A CN114605979A (en) | 2022-01-28 | 2022-01-28 | Calcium carbonate scale inhibitor for oil field and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210107610.6A CN114605979A (en) | 2022-01-28 | 2022-01-28 | Calcium carbonate scale inhibitor for oil field and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114605979A true CN114605979A (en) | 2022-06-10 |
Family
ID=81859285
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210107610.6A Pending CN114605979A (en) | 2022-01-28 | 2022-01-28 | Calcium carbonate scale inhibitor for oil field and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114605979A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104520405A (en) * | 2012-06-07 | 2015-04-15 | 利兹大学 | Method of inhibiting scale in geological formation |
| CN108949118A (en) * | 2018-08-16 | 2018-12-07 | 苏州火睿新材料科技有限公司 | The water-free cooling and preparation method thereof of hydroxyl fullerene |
-
2022
- 2022-01-28 CN CN202210107610.6A patent/CN114605979A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104520405A (en) * | 2012-06-07 | 2015-04-15 | 利兹大学 | Method of inhibiting scale in geological formation |
| CN108949118A (en) * | 2018-08-16 | 2018-12-07 | 苏州火睿新材料科技有限公司 | The water-free cooling and preparation method thereof of hydroxyl fullerene |
Non-Patent Citations (2)
| Title |
|---|
| 董雪铃: ""聚天冬氨酸共聚物的合成工艺研究"", 《石油化工》 * |
| 郑林萍: ""柠檬酸改性聚天冬氨酸阻垢剂的合成及性能研究"", 《环境科学与技术》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yang et al. | Synthesis and scale inhibition performance of a novel environmental friendly and hydrophilic terpolymer inhibitor | |
| Xu et al. | Synthesis of polyaspartic acid–melamine grafted copolymer and evaluation of its scale inhibition performance and dispersion capacity for ferric oxide | |
| Popov et al. | A comparative performance evaluation of some novel “green” and traditional antiscalants in calcium sulfate scaling | |
| US5776875A (en) | Use of biodegradable polymers in preventing scale build-up | |
| KR101751587B1 (en) | Process for the preparation of an aqueous solution comprising at least one earth alkali hydrogen carbonate and its use | |
| BR112014017679B1 (en) | process for the preparation of an aqueous solution, use of an aqueous solution, and, process for the mineralization of water | |
| AU2016200974A1 (en) | Thermally stable scale inhibitor compositions | |
| EP0206814A2 (en) | Water-soluble polymers and their use in the stabilization of aqueous systems | |
| CN102115265A (en) | Special compound type antisludging agent for seawater desalinization by hot method | |
| Matty et al. | Effect of multiple precipitation inhibitors on calcium carbonate nucleation | |
| JPS6015413A (en) | Novel scale-inhibiting copolymer and scale deposition inhibiting method | |
| CN105084561B (en) | Non-phosphorus scale and corrosion inhibitor containing fulvic acid and preparation method thereof | |
| BR102014010005B1 (en) | PROCESS FOR OBTAINING RANDOM COPOLYMERS, COPOLYMER, AND, USE OF A COPOLYMER | |
| Spinthaki et al. | Chemical methods for scaling control | |
| Popov et al. | DLS study of a phosphonate induced gypsum scale inhibition mechanism using indifferent nanodispersions as the standards for light scattering intensity comparison | |
| US20220275126A1 (en) | Processs to obtain random terpolymers derived from itaconic acid, aconitic acid and/or its isomers, and alkenyl sulfonates and use of the product thereof | |
| Liu | Research on performance evaluation and anti-scaling mechanism of green scale inhibitors by static and dynamic methods | |
| Shemer et al. | 13 Review of the State of the Art of Antiscalant Selection | |
| Liu et al. | Preparation and application of a phosphorous free and nonnitrogen scale inhibitor in industrial cooling water systems | |
| CN114605979A (en) | Calcium carbonate scale inhibitor for oil field and preparation method thereof | |
| JPS62129136A (en) | Stabilization of aqueous system | |
| US20070151927A1 (en) | Metal oxides dispersant composition | |
| ES2332266T3 (en) | DERIVATIVES OF POLYAMINOMETILENPHOSPHONATE. | |
| US20220332616A1 (en) | Treatment of aqueous systems | |
| Tlili et al. | Optimization of the preliminary treatment in a desalination plant by reverse osmosis |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220610 |