CN117511527A - Descaling blocking remover and preparation method thereof - Google Patents
Descaling blocking remover and preparation method thereof Download PDFInfo
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- CN117511527A CN117511527A CN202410000070.0A CN202410000070A CN117511527A CN 117511527 A CN117511527 A CN 117511527A CN 202410000070 A CN202410000070 A CN 202410000070A CN 117511527 A CN117511527 A CN 117511527A
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- descaling
- crown ether
- blocking remover
- sodium
- chelating
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- 230000000903 blocking effect Effects 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 33
- -1 aza crown ether Chemical class 0.000 claims description 56
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 42
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 42
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 239000002262 Schiff base Substances 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 25
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
- 239000002738 chelating agent Substances 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000004927 clay Substances 0.000 claims description 13
- 239000003381 stabilizer Substances 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 10
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000007810 chemical reaction solvent Substances 0.000 claims description 8
- PVBRSNZAOAJRKO-UHFFFAOYSA-N ethyl 2-sulfanylacetate Chemical compound CCOC(=O)CS PVBRSNZAOAJRKO-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000000605 extraction Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- KTOIESNTVCLSFG-UHFFFAOYSA-N 1-chloropropan-2-ol;sodium Chemical compound [Na].CC(O)CCl KTOIESNTVCLSFG-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- VWCFCFOIUSKKSC-UHFFFAOYSA-N ethane-1,2-diamine;2-hydroxy-1,3,2$l^{5}-dioxaphosphepane 2-oxide Chemical compound NCCN.OP1(=O)OCCCCO1 VWCFCFOIUSKKSC-UHFFFAOYSA-N 0.000 claims description 6
- 239000012074 organic phase Substances 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- 229940090960 diethylenetriamine pentamethylene phosphonic acid Drugs 0.000 claims description 3
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 3
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 3
- FDGBQHCDMSYZRC-UHFFFAOYSA-N 2-hydroxy-2-oxo-1,3,2$l^{5}-dioxaphosphinan-4-amine Chemical compound NC1CCOP(O)(=O)O1 FDGBQHCDMSYZRC-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 2
- 235000019830 sodium polyphosphate Nutrition 0.000 claims description 2
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 abstract description 54
- 238000005260 corrosion Methods 0.000 abstract description 23
- 230000007797 corrosion Effects 0.000 abstract description 23
- 125000003118 aryl group Chemical group 0.000 abstract description 3
- 125000000623 heterocyclic group Chemical group 0.000 abstract description 3
- 229910001422 barium ion Inorganic materials 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 8
- 239000013522 chelant Substances 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002332 oil field water Substances 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- TZLNJNUWVOGZJU-UHFFFAOYSA-M sodium;3-chloro-2-hydroxypropane-1-sulfonate Chemical compound [Na+].ClCC(O)CS([O-])(=O)=O TZLNJNUWVOGZJU-UHFFFAOYSA-M 0.000 description 2
- UBXAKNTVXQMEAG-UHFFFAOYSA-L strontium sulfate Chemical compound [Sr+2].[O-]S([O-])(=O)=O UBXAKNTVXQMEAG-UHFFFAOYSA-L 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000008398 formation water Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002455 scale inhibitor Substances 0.000 description 1
- 229910001427 strontium ion Inorganic materials 0.000 description 1
- HMNUYYJYMOXWTN-UHFFFAOYSA-J strontium;barium(2+);disulfate Chemical compound [Sr+2].[Ba+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HMNUYYJYMOXWTN-UHFFFAOYSA-J 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229960001082 trimethoprim Drugs 0.000 description 1
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
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
The invention relates to the technical field of blocking remover, and discloses a descaling blocking remover and a preparation method thereof. The aza-crown ether chelating main agent contains heat resistance, aromatic ring structure and heterocyclic structure of aza-crown ether, and has good structural stability at high temperature, good corrosion rate and blocking removal performance for barium sulfate.
Description
Technical Field
The invention relates to the technical field of blocking remover, in particular to a descaling blocking remover and a preparation method thereof.
Background
In low permeability oil field exploitation, oil gas exploitation amount can be improved by adopting an oil field water injection mode, but the oil field water injection contains a large amount of inorganic salt, and is combined with barium ions and strontium ions in formation water to form barium strontium sulfate precipitation dirt in equipment such as a shaft, a pipeline and the like, and the normal production of an oil gas well can be seriously influenced by the scaling of an oil-water well, so that equipment loss is caused by serious equipment loss, and potential safety hazards of production operation exist. Therefore, a novel blocking remover needs to be developed to remove and unblock precipitated dirt such as barium sulfate and the like generated in the process of oilfield exploitation operation.
The blocking remover generally comprises a chelating agent, a scale inhibitor, inorganic acid and the like, wherein the chelating agent is critical to the performance of the blocking remover, chinese patent CN105112036B discloses that organic amine and epoxy chloropropane are reacted to prepare a polyamine intermediate, and then the polyamine intermediate is reacted with chloroacetic acid and alkali to prepare an amine carboxylate solution which is used as the main component of the calcium scale remover and has good removal effect on insoluble salts such as barium sulfate, strontium sulfate and the like. However, when the stratum oil field is mined, the conventional blocking remover is poor in heat resistance due to higher stratum temperature, and the descaling and blocking removing performance of the blocking remover can be influenced.
Disclosure of Invention
The technical problems to be solved are as follows: the descaling blocking remover is prepared, and solves the problems that the traditional blocking remover has poor performance at high temperature and poor dirt removing effect on barium sulfate and the like.
The technical scheme is as follows: the descaling blocking remover comprises the following components in parts by weight: 48-74 parts of aza crown ether chelating main agent, 15-25 parts of phosphoric acid chelating agent, 6-14 parts of clay stabilizer HJZ-500, 4-10 parts of hydrochloric acid and 1-3 parts of acetic acid; the chemical structural formula of the aza crown ether chelating main agent is as follows:
。
wherein the phosphoric acid chelating agent comprises sodium polyphosphate, sodium hexametaphosphate, sodium pyrophosphate, aminotrimethylene phosphate, ethylenediamine tetramethylene phosphate and diethylenetriamine pentamethylene phosphonic acid.
Wherein the concentration of hydrochloric acid is 25-37%, and the concentration of acetic acid is more than or equal to 99%.
The preparation method of the descaling blocking remover comprises the following steps:
s1: adding a reaction solvent, schiff base aza crown ether and 3-chlorine-2-hydroxy propane sodium sulfonate into a flask, stirring for dissolving, dripping sodium hydroxide aqueous solution, stirring for reacting, adding water and methylene dichloride for extraction, oscillating uniformly, extracting for separation, drying an organic phase, and concentrating to obtain hydroxy propane sodium sulfonate Schiff base aza crown ether.
S2: adding a reaction solvent, sodium hydroxy propane sulfonate Schiff base aza crown ether and ethyl thioglycolate into a flask, reacting for 6-18h at 60-90 ℃, concentrating to remove the solvent, washing the product by acetone, dissolving in a sodium hydroxide aqueous solution, refluxing for 4-8h at 90-100 ℃, then dripping a hydrochloric acid solution to adjust the pH value to 3-4, heating to volatilize and remove water until a large amount of precipitate is separated out, filtering, washing by acetone, and obtaining the aza crown ether chelating main agent.
S3: adding the aza crown ether chelating main agent, the phosphoric acid chelating agent and the clay stabilizer HJZ-500 into deionized water, uniformly stirring, then dropwise adding acetic acid and hydrochloric acid, and uniformly mixing to obtain the descaling and blocking remover.
Wherein the reaction solvent in S1 comprises 1, 4-dioxane, dimethyl sulfoxide and N, N-dimethylformamide.
Wherein the molar ratio of the Schiff base aza crown ether, the 3-chloro-2-hydroxy propane sodium sulfonate and the sodium hydroxide in the S1 is 1:2.4-3:2.8-3.2.
Wherein the reaction temperature in S1 is between 60 and 80 ℃ and the reaction time is between 4 and 12 hours.
Wherein the reaction solvent in S2 comprises ethanol, dichloromethane, chloroform, benzene and toluene.
Wherein the molar ratio of the sodium hydroxy propane sulfonate Schiff base aza crown ether to the ethyl thioglycolate in the S2 is 1 (4.4-5.2).
The technical effects are as follows: the invention uses 3-chlorine-2-hydroxy propane sodium sulfonate and Schiff base aza crown ether to carry out substitution reaction, then the imine double bond of the 3-chlorine-2-hydroxy propane sodium sulfonate and Schiff base aza crown ether are subjected to addition reaction with thioglycollic acid ethyl ester, finally ester groups are hydrolyzed to obtain aza crown ether chelating main agent, and then the aza crown ether chelating main agent is compatible with phosphoric acid chelating agent, clay stabilizer, hydrochloric acid and the like to obtain the descaling blocking remover.
The aza crown ether chelating main agent contains aza crown ether chelating groups, has strong coordination bond with barium ions, can form stable coordination chelate, contains carboxyl, hydroxyl, sulfonic acid and other groups, can further improve the chelating ability with the barium ions, effectively inhibits barium ion crystallization and forms precipitated dirt, has excellent corrosion rate on barium sulfate polymer, and has excellent blocking removal performance.
The aza crown ether chelating main agent disclosed by the invention contains heat resistance, an aromatic ring structure and a heterocyclic structure of aza crown ether, has good structural stability at high temperature, can form a stable chelate ring structure after being chelated with barium ions, and can inhibit barium ions from crystallizing and forming precipitated dirt at high temperature, so that the descaling blocking remover has good corrosion rate and blocking removal performance on barium sulfate at high temperature.
Detailed Description
The preparation method of the Schiff base aza crown ether comprises the following steps: adding 0.05mol of hydroxyl-terminated benzaldehyde and 0.05mol of potassium carbonate into N, N-dimethylformamide, heating to 80 ℃ in toluene at room temperature for 1h, adding 0.025mol of dichloroethane, reacting for 2h, concentrating under reduced pressure, adding water, standing for 12h, filtering, adding the product into ethanol, decoloring and recrystallizing with activated carbon, filtering, and drying to obtain the 4, 4-diformyl-diphenylethane intermediate.
Adding tetrahydrofuran solution containing 5mmol of 4, 4-diformyl-diphenylethane intermediate and ethanol solution containing 5mmol of diethylenetriamine into ethanol, reacting for 24 hours at room temperature, filtering, washing with mixed solution of ethanol and tetrahydrofuran, and drying to obtain Schiff base aza crown ether with a structural formula of。
Example 1
S1: 1L of 1, 4-dioxane, 0.05mol of Schiff base aza crown ether and 0.12mol of 3-chloro-2-hydroxy propane sodium sulfonate are added into a flask, stirring and dissolving are carried out, 80mL of aqueous solution containing 0.12mol of sodium hydroxide is dropwise added, stirring and reflux reaction is carried out for 12 hours at 70 ℃, water and dichloromethane are added for extraction, shaking is carried out evenly, extraction separation is carried out, and organic phase is dried and concentrated, thus obtaining the hydroxy propane sodium sulfonate Schiff base aza crown ether. The reaction formula:
。
s2: adding 0.5L toluene, 0.05mol of sodium hydroxy propane sulfonate Schiff base aza crown ether and 0.22mol of ethyl thioglycolate into a flask, reacting for 6 hours at 60 ℃, concentrating to remove the solvent, washing the product by acetone, dissolving in a 6% sodium hydroxide aqueous solution, refluxing for 8 hours at 90 ℃, then dropwise adding a hydrochloric acid solution to adjust the pH to 4, heating to volatilize and remove water until a large amount of precipitate is separated out, filtering, washing by acetone, and obtaining the aza crown ether chelating main agent. The reaction formula:
。
s3: 48g of aza crown ether chelating main agent, 25g of ethylenediamine tetramethylene phosphoric acid chelating agent and 14g of clay stabilizer HJZ-500 are added into 600mL of deionized water, uniformly stirred, and then 3g of acetic acid with the concentration of 99.5% and 10g of hydrochloric acid with the concentration of 25% are added dropwise to obtain the descaling and blocking remover.
Example 2
S1: adding 0.5L of dimethyl sulfoxide, 0.05mol of Schiff base aza crown ether and 0.15mol of 3-chloro-2-hydroxy propane sodium sulfonate into a flask, stirring for dissolving, dripping 80mL of aqueous solution containing 0.16mol of sodium hydroxide, stirring for reflux reaction for 12h at 60 ℃, adding water and methylene chloride for extraction, oscillating uniformly, extracting and separating, drying an organic phase, and concentrating to obtain the hydroxy propane sodium sulfonate Schiff base aza crown ether.
S2: adding 1L of dichloromethane, 0.05mol of sodium hydroxy propane sulfonate Schiff base aza crown ether and 0.26mol of ethyl thioglycolate into a flask, reacting for 18 hours at 80 ℃, concentrating to remove a solvent, washing a product by acetone, dissolving the product in a 6% sodium hydroxide aqueous solution, refluxing for 4 hours at 100 ℃, then dropwise adding a hydrochloric acid solution to adjust the pH to 4, heating to volatilize and remove water until a large amount of precipitate is separated out, filtering, washing by acetone, and obtaining the aza crown ether chelating main agent.
S3: 53g of aza crown ether chelating main agent, 25g of diethylenetriamine penta methylene phosphonic acid chelating agent and 12g of clay stabilizer HJZ-500 are added into 600mL of deionized water, evenly stirred, and then 2g of acetic acid with the concentration of 99.5% and 8g of hydrochloric acid with the concentration of 25% are added dropwise to obtain the descaling and blocking removing agent.
Example 3
S1: adding 0.5L of dimethyl sulfoxide, 0.05mol of Schiff base aza crown ether and 0.12mol of 3-chloro-2-hydroxy propane sodium sulfonate into a flask, stirring for dissolving, dripping 80mL of aqueous solution containing 0.14mol of sodium hydroxide, stirring for reflux reaction for 4 hours at 80 ℃, adding water and methylene chloride for extraction, oscillating uniformly, extracting and separating, drying an organic phase, and concentrating to obtain the hydroxy propane sodium sulfonate Schiff base aza crown ether.
S2: adding 1L of ethanol, 0.05mol of sodium hydroxy propane sulfonate Schiff base aza crown ether and 0.24mol of ethyl thioglycolate into a flask, reacting for 6 hours at 90 ℃, concentrating to remove a solvent, washing a product by acetone, dissolving the product in a 6% sodium hydroxide aqueous solution, refluxing for 4 hours at 100 ℃, then dropwise adding a hydrochloric acid solution to adjust the pH to 3, heating to volatilize and remove water until a large amount of precipitate is separated out, filtering, washing by acetone, and obtaining the aza crown ether chelating main agent.
S3: 64g of aza crown ether chelating main agent, 18g of amino trimethoprim chelating agent and 10g of clay stabilizer HJZ-500 are added into 600mL of deionized water, and evenly stirred, then 2g of acetic acid with the concentration of 99.5% and 6g of hydrochloric acid with the concentration of 30% are added dropwise, thus obtaining the descaling and blocking remover.
Example 4
S1: adding 0.8L of N, N-dimethylformamide, 0.05mol of Schiff base aza crown ether and 0.14mol of 3-chloro-2-hydroxy propane sodium sulfonate into a flask, stirring for dissolution, dropwise adding 80mL of aqueous solution containing 0.16mol of sodium hydroxide, stirring and refluxing at 60 ℃ for reaction for 12 hours, adding water and dichloromethane for extraction, oscillating uniformly, extracting and separating, drying an organic phase, and concentrating to obtain the hydroxy propane sodium sulfonate Schiff base aza crown ether.
S2: adding 0.5L of chloroform, 0.05mol of sodium hydroxy propane sulfonate Schiff base aza crown ether and 0.22mol of ethyl thioglycolate into a flask, reacting for 18 hours at 80 ℃, concentrating to remove a solvent, washing a product by acetone, dissolving in a 6% sodium hydroxide aqueous solution, refluxing for 8 hours at 90 ℃, then dropwise adding a hydrochloric acid solution to adjust the pH to 4, heating to volatilize and remove water until a large amount of precipitate is separated out, filtering, washing by acetone, and obtaining the aza crown ether chelating main agent. The structural formula is as follows:
。
s3: 74g of aza crown ether chelating main agent, 15g of sodium hexametaphosphate chelating agent and 6g of clay stabilizer HJZ-500 are added into 600mL of deionized water, and are stirred uniformly, and then 1g of acetic acid with the concentration of 99.5% and 4g of hydrochloric acid with the concentration of 37% are added dropwise to obtain the descaling blocking remover.
Comparative example 1
48g of Schiff base aza crown ether) As a main agent, 25g of ethylenediamine tetramethylene phosphate chelating agent and 14g of clay stabilizer HJZ-500 are added into 600mL of deionized water, and the mixture is stirred uniformly, and then 3g of acetic acid with the concentration of 99.5% and 10g of hydrochloric acid with the concentration of 25% are added dropwise to obtain the descaling and blocking remover.
Comparative example 2
48g of sodium hydroxy propane sulfonate Schiff base aza crown ether) As a main agent, 25g of ethylenediamine tetramethylene phosphate chelating agent and 14g of clay stabilizer HJZ-500 are added into 600mL of deionized water, and the mixture is stirred uniformly, and then 3g of acetic acid with the concentration of 99.5% and 10g of hydrochloric acid with the concentration of 25% are added dropwise to obtain the descaling and blocking remover.
Comparative example 3
48g of sodium 3-chloro-2-hydroxy propane sulfonate) Adding 25g of ethylenediamine tetramethylene phosphate chelating agent and 14g of clay stabilizer HJZ-500 serving as main agents into 600mL of deionized water, uniformly stirring, and then drippingAdding 3g of acetic acid with the concentration of 99.5 percent and 10g of hydrochloric acid with the concentration of 25 percent to obtain the descaling and blocking remover.
Comparative example 4
48g of thioglycollic acid is used as a main agent) 25g of ethylenediamine tetramethylene phosphate chelating agent and 14g of clay stabilizer HJZ-500 are added into 600mL of deionized water, uniformly stirred, and then 3g of acetic acid with the concentration of 99.5% and 10g of hydrochloric acid with the concentration of 25% are added dropwise to obtain the descaling and blocking remover.
Barium sulfate is used for simulating oil-water well scaling, barium sulfate with different quality is respectively added into the descaling and blocking remover, the proportion of the barium sulfate and the descaling and blocking remover is controlled to be Q, stirring is carried out for 6 hours at 40 ℃ for corrosion, the stirring rotating speed is controlled to be 30r/min, the solution is filtered, the residual barium sulfate is washed by water, and the solution is dried, weighed and the corrosion rate W is calculated. W= (m 0 -m 1 ）/m 0 。m 0 Is the mass, m, of barium sulfate before corrosion 1 Is the mass of barium sulfate after corrosion. The higher the corrosion rate is, the better the plugging removal performance of the descaling plugging remover is.
Table 1 scale removal blocking remover blocking removal performance test 1
Barium sulfate is used for simulating oil-water well scaling, barium sulfate with different quality is respectively added into the descaling blocking remover, the proportion of the barium sulfate to the descaling blocking remover is controlled to be 40g/L, stirring is carried out for different time at 40 ℃ for corrosion, the stirring rotating speed is controlled to be 30r/min, the solution is filtered, the residual barium sulfate is washed by water, and the solution is dried, weighed and the corrosion rate W is calculated. W= (m 0 -m 1 ）/m 0 。m 0 Is the mass, m, of barium sulfate before corrosion 1 Is the mass of barium sulfate after corrosion. The higher the corrosion rate is, the better the plugging removal performance of the descaling plugging remover is.
Table 2 scale removal blocking remover blocking removal performance test 2
Examples 1 to 4 were formulated with an aza-crown ether chelating agent, a phosphoric acid chelating agent, a salt, etc., and the obtained descaling blocking remover exhibited excellent corrosion rate to barium sulfate and excellent blocking removing performance, because the aza-crown ether chelating agent contained an aza-crown ether chelating group, had a strong coordination bond with barium ion, formed a stable coordination chelate, and the aza-crown ether chelating agent contained a carboxyl group, hydroxyl group, sulfonic acid, etc., and thus the chelating ability with barium ion was further improved, and barium ion crystallization and formation of precipitated scale were effectively suppressed.
In the comparative example 1, schiff base aza crown ether is used as a main agent of a descaling and blocking remover, and does not contain carboxyl, sulfonic acid, hydroxyl and other groups; in comparative example 2, sodium hydroxy propane sulfonate Schiff base aza crown ether is used as a main agent of a descaling and blocking remover, does not contain carboxyl groups, has poor chelating ability with barium ions, cannot effectively inhibit barium ions from crystallizing and forming precipitated dirt, and has lower corrosion rate on barium sulfate than that of example 1.
Comparative example 3 uses sodium 3-chloro-2-hydroxy propane sulfonate as the main agent and comparative example 4 thioglycollic acid as the main agent, does not contain aza crown ether chelate structure, and has the worst corrosion rate and blocking removal performance.
Barium sulfate is used for simulating oil-water well scaling, barium sulfate with different quality is respectively added into a descaling and blocking remover, the proportion of the barium sulfate to the descaling and blocking remover is controlled to be 40g/L, stirring is carried out for 24 hours at different temperatures for corrosion, the stirring rotating speed is controlled to be 30r/min, the solution is filtered, the residual barium sulfate is washed by water, and the solution is dried, weighed and the corrosion rate W is calculated. W= (m 0 -m 1 ）/m 0 。m 0 Is the mass, m, of barium sulfate before corrosion 1 Is the mass of barium sulfate after corrosion. The higher the corrosion rate is, the better the plugging removal performance of the descaling plugging remover is.
Table 3 scale removal blocking remover blocking removal performance test 3
Examples 1 to 4 chelate the main agent with aza crown ether, and the obtained descaling and blocking remover has good corrosion effect on barium sulfate and good corrosion rate and blocking removal performance at a high temperature of 80 ℃. This is because the aza-crown ether chelating main agent contains heat resistance, an aromatic ring structure and a heterocyclic structure of aza-crown ether, and the aza-crown ether chelating main agent also has good structural stability at high temperature, and can form a stable chelate ring structure after chelating with barium ions, and can inhibit barium ions from crystallizing and forming precipitated dirt at high temperature.
Claims (9)
1. The descaling blocking remover is characterized by comprising the following components in parts by weight: 48-74 parts of aza crown ether chelating main agent, 15-25 parts of phosphoric acid chelating agent, 6-14 parts of clay stabilizer HJZ-500, 4-10 parts of hydrochloric acid and 1-3 parts of acetic acid; the chemical structural formula of the aza crown ether chelating main agent is as follows:
。
2. the descaling blocking remover according to claim 1, wherein the phosphate chelating agent comprises sodium polyphosphate, sodium hexametaphosphate, sodium pyrophosphate, aminotrimethylene phosphate, ethylenediamine tetramethylene phosphate, diethylenetriamine pentamethylene phosphonic acid.
3. The descaling blocking remover according to claim 1, wherein the concentration of hydrochloric acid is 25-37% and the concentration of acetic acid is not less than 99%.
4. A method for preparing the descaling blocking remover according to any of claims 1-3, comprising the steps of:
s1: adding a reaction solvent, schiff base aza crown ether and 3-chlorine-2-hydroxy propane sodium sulfonate into a flask, stirring for dissolving, dripping sodium hydroxide aqueous solution, stirring for reacting, adding water and methylene dichloride for extraction, oscillating uniformly, extracting for separation, drying an organic phase, and concentrating to obtain hydroxy propane sodium sulfonate Schiff base aza crown ether;
s2: adding a reaction solvent, sodium hydroxy propane sulfonate Schiff base aza crown ether and ethyl thioglycolate into a flask, reacting for 6-18 hours at 60-90 ℃, concentrating to remove the solvent, washing the product by acetone, dissolving in a sodium hydroxide aqueous solution, refluxing for 4-8 hours at 90-100 ℃, then dripping a hydrochloric acid solution to adjust the pH value to 3-4, heating to volatilize and remove water until a large amount of precipitate is separated out, filtering, washing by acetone, and obtaining the aza crown ether chelating main agent;
s3: adding the aza crown ether chelating main agent, the phosphoric acid chelating agent and the clay stabilizer into deionized water, uniformly stirring, then dropwise adding acetic acid and hydrochloric acid, and uniformly mixing to obtain the descaling and blocking remover.
5. The method for preparing a descaling blocking remover according to claim 4, wherein the reaction solvent in S1 comprises 1, 4-dioxane, dimethyl sulfoxide, and N, N-dimethylformamide.
6. The method for preparing the descaling blocking remover according to claim 4, wherein the molar ratio of the Schiff base aza crown ether, the 3-chloro-2-hydroxy propane sodium sulfonate and the sodium hydroxide in the S1 is 1:2.4-3:2.8-3.2.
7. The method for preparing the descaling blocking remover according to claim 4, wherein the reaction temperature in the step S1 is 60-80 ℃ and the reaction time is 4-12 h.
8. The method for preparing the descaling blocking remover according to claim 4, wherein the reaction solvent in the step S2 comprises ethanol, dichloromethane, chloroform, benzene and toluene.
9. The method for preparing the descaling blocking remover according to claim 4, wherein the molar ratio of the sodium hydroxy propane sulfonate Schiff base aza crown ether to the ethyl thioglycolate in the S2 is 1 (4.4-5.2).
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