CN117866606A - Chemical agent composition containing phloroglucinol polyether and thickened oil CO 2 Throughput viscosity-reducing and efficiency-increasing method - Google Patents
Chemical agent composition containing phloroglucinol polyether and thickened oil CO 2 Throughput viscosity-reducing and efficiency-increasing method Download PDFInfo
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- CN117866606A CN117866606A CN202211247963.2A CN202211247963A CN117866606A CN 117866606 A CN117866606 A CN 117866606A CN 202211247963 A CN202211247963 A CN 202211247963A CN 117866606 A CN117866606 A CN 117866606A
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- phloroglucinol
- polyether
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- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 title claims abstract description 102
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 229960001553 phloroglucinol Drugs 0.000 title claims abstract description 102
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 71
- 229920000570 polyether Polymers 0.000 title claims abstract description 71
- 239000000203 mixture Substances 0.000 title claims abstract description 58
- 239000013043 chemical agent Substances 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 24
- -1 triazole ester Chemical class 0.000 claims abstract description 110
- 230000009467 reduction Effects 0.000 claims abstract description 14
- 230000001603 reducing effect Effects 0.000 claims abstract description 6
- 230000002708 enhancing effect Effects 0.000 claims abstract description 4
- 239000003921 oil Substances 0.000 claims description 113
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 51
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 41
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 238000002360 preparation method Methods 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 34
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- 230000015572 biosynthetic process Effects 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 15
- 239000000295 fuel oil Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- 239000012954 diazonium Substances 0.000 claims description 7
- 230000001965 increasing effect Effects 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 150000001540 azides Chemical class 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 5
- 238000010791 quenching Methods 0.000 claims description 5
- 239000001632 sodium acetate Substances 0.000 claims description 5
- 235000017281 sodium acetate Nutrition 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 150000001989 diazonium salts Chemical class 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 3
- 150000001413 amino acids Chemical class 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 2
- 239000007810 chemical reaction solvent Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 235000010378 sodium ascorbate Nutrition 0.000 claims description 2
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 claims description 2
- 229960005055 sodium ascorbate Drugs 0.000 claims description 2
- MFBOGIVSZKQAPD-UHFFFAOYSA-M sodium butyrate Chemical compound [Na+].CCCC([O-])=O MFBOGIVSZKQAPD-UHFFFAOYSA-M 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- JXKPEJDQGNYQSM-UHFFFAOYSA-M sodium propionate Chemical compound [Na+].CCC([O-])=O JXKPEJDQGNYQSM-UHFFFAOYSA-M 0.000 claims description 2
- 235000010334 sodium propionate Nutrition 0.000 claims description 2
- 239000004324 sodium propionate Substances 0.000 claims description 2
- 229960003212 sodium propionate Drugs 0.000 claims description 2
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical group [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims 1
- 238000004090 dissolution Methods 0.000 abstract description 14
- 238000011084 recovery Methods 0.000 abstract description 10
- 238000006073 displacement reaction Methods 0.000 abstract description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 46
- 150000002430 hydrocarbons Chemical group 0.000 description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 15
- 239000010779 crude oil Substances 0.000 description 13
- 229920001451 polypropylene glycol Polymers 0.000 description 13
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 239000010426 asphalt Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- 150000007942 carboxylates Chemical class 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- DWAYENIPKPKKMV-ILKKLZGPSA-N [(2s)-3-(1h-imidazol-3-ium-4-yl)-1-methoxy-1-oxopropan-2-yl]azanium;dichloride Chemical compound Cl.Cl.COC(=O)[C@@H](N)CC1=CN=CN1 DWAYENIPKPKKMV-ILKKLZGPSA-N 0.000 description 3
- 229940072107 ascorbate Drugs 0.000 description 3
- 235000010323 ascorbic acid Nutrition 0.000 description 3
- 239000011668 ascorbic acid Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 3
- 238000003810 ethyl acetate extraction Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- CMCBDXRRFKYBDG-UHFFFAOYSA-N 1-dodecoxydodecane Chemical compound CCCCCCCCCCCCOCCCCCCCCCCCC CMCBDXRRFKYBDG-UHFFFAOYSA-N 0.000 description 2
- HANWHVWXFQSQGJ-UHFFFAOYSA-N 1-tetradecoxytetradecane Chemical compound CCCCCCCCCCCCCCOCCCCCCCCCCCCCC HANWHVWXFQSQGJ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- SBBWEQLNKVHYCX-UHFFFAOYSA-N ethyl 2-amino-3-(4-hydroxyphenyl)propanoate Chemical compound CCOC(=O)C(N)CC1=CC=C(O)C=C1 SBBWEQLNKVHYCX-UHFFFAOYSA-N 0.000 description 2
- FMVJYQGSRWVMQV-UHFFFAOYSA-N ethyl propiolate Chemical compound CCOC(=O)C#C FMVJYQGSRWVMQV-UHFFFAOYSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 1
- YAYNEUUHHLGGAH-UHFFFAOYSA-N 1-chlorododecane Chemical compound CCCCCCCCCCCCCl YAYNEUUHHLGGAH-UHFFFAOYSA-N 0.000 description 1
- RNHWYOLIEJIAMV-UHFFFAOYSA-N 1-chlorotetradecane Chemical compound CCCCCCCCCCCCCCCl RNHWYOLIEJIAMV-UHFFFAOYSA-N 0.000 description 1
- CENDNMFHRRPMJG-UHFFFAOYSA-N 2,5-dichloro-n-ethylaniline Chemical compound CCNC1=CC(Cl)=CC=C1Cl CENDNMFHRRPMJG-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 229940024606 amino acid Drugs 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000003027 oil sand Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- 238000000196 viscometry Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Classifications
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- 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
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/588—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific polymers
-
- 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
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/594—Compositions used in combination with injected gas, e.g. CO2 orcarbonated gas
-
- 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
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
-
- 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
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
- E21B43/164—Injecting CO2 or carbonated water
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mining & Mineral Resources (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Fluid Mechanics (AREA)
- Physics & Mathematics (AREA)
- Geochemistry & Mineralogy (AREA)
- Environmental & Geological Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention relates to a chemical agent composition containing phloroglucinol polyether and thick oil CO 2 A method for reducing the viscosity and enhancing the efficiency of throughput. The chemical agent composition comprises phloroglucinol polyether and triazole ester; wherein the phloroglucinol polyether is selected from structures shown in formula (I), and the triazole ester is selected from structures shown in formula (II):the chemical agent composition is directly dissolved in supercritical CO 2 Is injected into stratum and reacts with CO under stratum condition 2 The thickened oil acts to increase CO 2 Solubility in thick oil and improving dissolution efficiency. The chemical agent assisted thickened oil CO 2 The viscosity reduction and synergy method can improve the CO of the thickened oil 2 Throughput efficiencyAnd the throughput period is shortened, the thickened oil exploitation cost is reduced, and the oil displacement recovery ratio is improved.
Description
Technical Field
The invention relates to the field of petroleum exploitation, in particular to a chemical agent composition containing phloroglucinol polyether and thick oil CO 2 The method for reducing viscosity and enhancing efficiency of throughput.
Background
The thick oil refers to crude oil with higher asphaltene and colloid content and higher viscosity. The viscosity of the oil layer is generally higher than 50 mPa.s and the density is higher than 0.92g/cm 3 Crude oil at (20 ℃) is known as thick oil. According to viscosity, the thick oil can be divided into three types of common thick oil (50-10000 mPa.s), extra thick oil (10000-50000 mPa.s) and super thick oil (more than 50000mPa.s natural asphalt).
The global thick oil and oil sand resources are huge, and the geological storage capacity is higher than the sum of the conventional oil and gas resources. The thick oil resources in China are also rich, the land thick oil and asphalt resources account for more than 20 percent of the total national petroleum resources, and are mainly distributed in victory oil fields, liaohe oil fields, henan oil fields, hong Kong oil fields and the like. At present, the exploitation mode of thick oil is mainly divided into two modes of hot exploitation and cold exploitation. The thick oil thermal recovery technology is a widely used recovery method, but for complex thick oil reservoirs such as hypotonic and water sensitive reservoirs, the thermal recovery method cannot realize effective recovery due to the influence of multiple factors such as high crude oil viscosity, low permeability and serious stratum injury.
CO 2 The method is easy to reach a supercritical state, has good dissolving capacity for crude oil, and is an ideal displacement medium. In recent years, emission reduction of greenhouse gases is increasingly high. In the emission reduction measures proposed by the international energy agency, the contribution of the CCUS technology is 20%. At present, however, the CO captured by CCUS technology 2 More than 70% of the catalyst is used for CO 2 And (3) driving an enhanced oil recovery project. CO 2 The EOR technology not only can improve the recovery ratio of the oil field, but also can seal a large amount of CO 2 Is a win-win measure for economic development and environmental protection.
Asphalt in thick oilHigh colloid content, and difficulty in mixing with CO under oil reservoir condition 2 Achieve mixed phase and can not carry out CO 2 And (5) phase mixing driving. However, CO 2 On one hand, the water-soluble polymer can expand the volume of the thick oil and increase the internal kinetic energy when being dissolved in the thick oil, on one hand, the viscosity of the thick oil can be greatly reduced, and the flowability of the thick oil is improved. CO 2 Throughput technology has been applied to heavy oil recovery as the most cost effective cold recovery method at present.
At present, thick oil CO 2 The difficulties of throughput techniques are mainly two: CO is one 2 The solubility in thick oil is low, resulting in low viscosity reduction. Second is CO 2 The dissolution rate in the thick oil is slow, resulting in long throughput period and low efficiency. In CO 2 Adding chemical agent to improve CO 2 The solubility and the dissolution speed in the thick oil are improved, the viscosity reduction rate is further improved, and the throughput period is shortened. Patent CN 110552671A discloses a method for assisting CO by using dimethyl ether 2 The method for realizing the high-efficiency development of the heavy oil reservoir by flooding. On one hand, dimethyl ether is dissolved in crude oil to greatly reduce the viscosity of the crude oil, and on the other hand, the dimethyl ether can reduce CO 2 Minimum miscible pressure with crude oil. Dimethyl ether and CO 2 The mixture is mixed together at a certain proportion on the ground to be injected into the heavy oil reservoir, so that the high-efficiency development of the heavy oil reservoir can be realized. However, the method has the advantages of larger dosage of the dimethyl ether, low economic benefit, low flash point of the dimethyl ether, inflammability and explosiveness, and larger potential safety hazard in the storage and use processes. Patent CN202010619848.8 (CN 113880716A) before the inventor discloses phloroglucinol polyether carboxylate and its composition, preparation method and deep low-permeability thick oil CO 2 The method for dispelling and reducing viscosity and enhancing efficiency. CO using phloroglucinol polyether carboxylates and compositions thereof 2 High-efficiency promotion of CO by amphipathic nature of crude oil 2 The crude oil is mutually dissolved, the dissolution efficiency is improved, and the CO of the thick oil is further improved 2 Throughput efficiency. However, the phloroglucinol polyether carboxylate is present in CO 2 The solubility in water is low, the dissolution pressure is high, and the addition of alkylphenol polyether auxiliary agent improves the CO content 2 But the dissolution pressure is still not low. Moreover, the dissolution pressure of the phloroglucinol polyether carboxylate composition tends to increase significantly with increasing temperature, so that its application is greatly limited.
Disclosure of Invention
To solve the thick oil CO 2 CO in throughput technology 2 The invention provides a chemical agent composition containing phloroglucinol polyether and triazole ester, which is directly dissolved in liquid or supercritical CO 2 Is injected into stratum and reacts with CO under stratum condition 2 The thickened oil acts to increase CO 2 Solubility in thick oil and improving dissolution efficiency.
One of the purposes of the invention is to provide a chemical agent composition containing phloroglucinol polyether, which comprises phloroglucinol polyether and triazole ester,
wherein the phloroglucinol polyether is at least one of structures shown in a formula (I):
in the formula (I), R 1 、R 2 、R 3 Independently selected from (CH) 2 ) j H, j is any integer from 0 to 4; a, a 1 、a 2 、a 3 Is substituted by R 1 The number of polyether groups b 1 、b 2 、b 3 Is substituted by R 2 The number of polyether groups c 1 、c 2 、c 3 Is substituted by R 3 The number of polyether groups; a, a 1 、a 2 、a 3 、b 1 、b 2 、b 3 、c 1 、c 2 、c 3 Independently is any integer from 0 to 50, and a 1+ a 2+ a 3+ b 1+ b 2+ b 3+ c 1+ c 2+ c 3 >0；X 1 、X 2 、X 3 Independently selected from hydrogen atoms, C 1 ～C 50 Is a hydrocarbon group or a substituted hydrocarbon group;
the triazole ester is at least one selected from structures shown in a formula (II):
in the formula (II), R 4 、R 5 、R 6 Independently is a hydrogen atom, C 1 ～C 50 Is a hydrocarbon group or a substituted hydrocarbon group; y is Y 1 、Y 2 、Y 3 Independently a hydrogen atom or COOR 7 And not simultaneously being hydrogen atoms, R 7 Is C 1 ～C 50 Is a hydrocarbon group or a substituted hydrocarbon group; n is n 1 、n 2 、n 3 Independently is any integer from 0 to 20.
According to a preferred embodiment of the invention, said R 1 、R 2 、R 3 Independently selected from (CH) 2 ) j H, j is any integer from 0 to 4, and R 1 、R 2 、R 3 Not both hydrogen atoms; a, a 1 、a 2 、a 3 、b 1 、b 2 、b 3 、c 1 、c 2 、c 3 Independently is any integer from 0 to 50, and a 1+ a 2+ a 3+ b 1+ b 2+ b 3+ c 1+ c 2+ c 3 >0；X 1 、X 2 、X 3 Independently selected from hydrogen atoms, C 1 ～C 50 Is a hydrocarbon group or a substituted hydrocarbon group;
R 4 、R 5 、R 6 independently is a hydrogen atom, C 1 ～C 50 Is a hydrocarbon group or a substituted hydrocarbon group; y is Y 1 、Y 2 、Y 3 Independently a hydrogen atom or COOR 7 And not simultaneously being hydrogen atoms, R 7 Is C 1 -a C50 hydrocarbyl or substituted hydrocarbyl group; n is n 1 、n 2 、n 3 Independently is any integer from 0 to 20.
According to a preferred embodiment of the invention, said R 1 、R 2 、R 3 Independently selected from (CH) 2 ) j H, j is any integer from 0 to 4, and R 1 、R 2 、R 3 Comprising at least two different groups; a, a 1 、a 2 、a 3 、b 1 、b 2 、b 3 、c 1 、c 2 、c 3 Independently is any integer from 0 to 50, and a 1+ a 2+ a 3 >0，b 1+ b 2+ b 3 >0，c 1+ c 2+ c 3 >0；X 1 、X 2 、X 3 Independently selected from hydrogen atoms, C 1 ～C 50 Is a hydrocarbon group or a substituted hydrocarbon group;
R 4 、R 5 、R 6 independently is a hydrogen atom, C 1 ～C 50 Is a hydrocarbon group or a substituted hydrocarbon group; y is Y 1 、Y 2 、Y 3 Independently a hydrogen atom or COOR 7 And not simultaneously being hydrogen atoms, R 7 Is C 1 -a C50 hydrocarbyl or substituted hydrocarbyl group; n is n 1 、n 2 、n 3 Independently is any integer from 0 to 20.
According to a preferred embodiment of the invention, said R 1 、R 2 、R 3 Independently selected from (CH) 2 ) j H, j is any integer from 1 to 4; a, a 1 、a 2 、a 3 、b 1 、b 2 、b 3 、c 1 、c 2 、c 3 Independently is any integer from 0 to 40, and a 1+ a 2+ a 3 >0，b 1+ b 2+ b 3 >0，c 1+ c 2+ c 3 >0；X 1 、X 2 、X 3 Independently selected from hydrogen atoms, C 1 ～C 40 Is a hydrocarbon group or a substituted hydrocarbon group;
R 4 、R 5 、R 6 independently is a hydrogen atom, C 1 ～C 30 Is a hydrocarbon group or a substituted hydrocarbon group; y is Y 1 、Y 2 、Y 3 Independently a hydrogen atom or COOR 7 And not simultaneously being hydrogen atoms, R 7 Is C 1 ～C 30 Is a hydrocarbon group or a substituted hydrocarbon group; n is n 1 、n 2 、n 3 Independently is any integer from 0 to 10.
In the above embodiment, preferably, the R 1 、R 2 、R 3 Independently selected from (CH) 2 ) j H, j is any integer from 1 to 3A number; a, a 1 、a 2 、a 3 、b 1 、b 2 、b 3 、c 1 、c 2 、c 3 Independently is any integer from 0 to 30, and a 1+ a 2+ a 3 >0，b 1+ b 2+ b 3 >0，c 1+ c 2+ c 3 >0；X 1 、X 2 、X 3 Independently selected from hydrogen atoms, C 5 ～C 30 Is a hydrocarbon group or a substituted hydrocarbon group;
R 4 、R 5 、R 6 independently is a hydrogen atom, C 1 ～C 30 Is a hydrocarbon group or a substituted hydrocarbon group; y is Y 1 、Y 2 、Y 3 Independently a hydrogen atom or COOR 7 And not simultaneously being hydrogen atoms, R 7 Is C 1 ～C 30 Is a hydrocarbon group or a substituted hydrocarbon group; n is n 1 、n 2 、n 3 Independently is any integer from 0 to 10.
More preferably in the above embodiment, the R 1 、R 2 、R 3 Independently selected from (CH) 2 ) j H, j is any integer from 1 to 3, and R 1 、R 2 、R 3 Comprising at least two different groups; a, a 1 、a 2 、a 3 、b 1 、b 2 、b 3 、c 1 、c 2 、c 3 Independently is any integer from 0 to 30, and a 1+ a 2+ a 3 >0，b 1+ b 2+ b 3 >0，c 1+ c 2+ c 3 >0；X 1 、X 2 、X 3 Independently selected from hydrogen atoms, C 5 ～C 30 Is a hydrocarbon group or a substituted hydrocarbon group;
R 4 、R 5 、R 6 independently is a hydrogen atom, C 1 ～C 30 Is a hydrocarbon group or a substituted hydrocarbon group; y is Y 1 、Y 2 、Y 3 Independently a hydrogen atom or COOR 7 And not simultaneously being hydrogen atoms, R 7 Is C 1 ～C 30 Is a hydrocarbon group or a substituted hydrocarbon group; n is n 1 、n 2 、n 3 Independently is any integer from 0 to 10.
According to a preferred embodiment of the invention, the molar ratio of the phloroglucinol polyether to the triazole ester is 1: (0.01 to 20), preferably 1: (0.05 to 10), for example, may be 1:0.01, 1:0.05, 1: 1. 1: 2. 1: 3. 1: 4. 1: 5. 1: 6. 1: 7. 1: 8. 1: 9. 1: 10. 1: 12. 1: 15. 1: 18. 1:20, etc.
It is a second object of the present invention to provide a process for preparing the chemical agent composition comprising mixing the phloroglucinol polyether with the triazole ester.
Wherein, the mol ratio of the phloroglucinol polyether to the triazole ester is 1: (0.01 to 20), preferably 1: (0.05-10).
The phloroglucinol polyether can be prepared by the following steps:
(1) under the action of alkali A, phloroglucinol reacts with epoxy compound to obtain X 1 、X 2 、X 3 A phloroglucinol polyether compound having hydrogen atoms;
optionally, (2) reacting a phloroglucinol polyether compound with R in the presence of a base B 8 Cl reaction to obtain the phloroglucinol polyether; wherein R is 8 Is C 1 ～C 50 Or a substituted hydrocarbon group.
In the preparation steps of the phloroglucinol polyether,
in the step (1), the reaction temperature is 100-140 ℃, the pressure is 0.10-0.40 MPa gauge pressure, the alkali A is at least one of sodium carbonate, sodium hydroxide and potassium hydroxide, the dosage of the alkali A is 0.5-5.0% of the mass of phloroglucinol, and the epoxy compounds include but are not limited to ethylene oxide, propylene oxide, butylene oxide and the like.
In the step (2), the reaction solvent is benzene or toluene, reflux reaction is carried out, the alkali B is at least one of sodium hydroxide and potassium hydroxide, and the molar ratio of the alkali B to the phloroglucinol polyether compound is preferably 1.0-2.0.
The triazolyl ester can be obtained by the following steps:
(1) ' amino compound or amino ester compound and NaNO in hydrochloric acid solution 2 Reacting to obtain diazonium salt;
(2) ' diazonium salts are weakAlkali solution and NaN 3 Reacting to generate an azide;
(3) the' alkynyl ester compound reacts with the azide compound in the presence of a copper catalyst and a reducing agent to obtain the triazole ester.
In the above preparation steps of the triazolyl ester,
in the step (1)' the reaction temperature is-8 to-3 ℃; the concentration of the hydrochloric acid solution is 2-6 mol/L; naNO 2 The molar ratio of the amino acid to the amino compound or the amino ester compound is 1 to 1.2; and adding urea for quenching after the reaction is finished, wherein the molar ratio of the urea to the amino compound or the amino ester compound is 0.1-0.12.
The amino compounds or amino ester compounds include, but are not limited to, histidine methyl ester dihydrochloride, L-tyrosine ethyl ester hydrochloride, and the like.
In the step (2)' the reaction temperature is-5 to 0 ℃; the weak base solution is at least one of sodium acetate, sodium propionate or sodium butyrate, and the concentration of the weak base solution is preferably 1.5-2.5 mol/L; naN (NaN) 3 The molar ratio of the amino compound to the amino ester compound is 1 to 1.2.
In the step (3)' the reaction temperature is normal temperature; the copper catalyst is selected from CuI, cuBr, cuSO 4 ·5H 2 At least one of O, wherein the molar ratio of the copper catalyst to the alkynyl ester compound is 0.05-0.1; the reducing agent is sodium ascorbate, and the molar ratio of the reducing agent to the alkynyl ester compound is 0.1-0.2; the molar ratio of the alkynyl ester compound to the azide compound is preferably 0.8 to 1.2.
The third object of the present invention is to provide a thick oil CO 2 The throughput viscosity reduction and synergy method comprises the steps of dissolving the chemical agent composition containing the phloroglucinol polyether in liquid and/or supercritical CO 2 Is injected into the formation together.
The dosage of the chemical agent composition is CO under the injection pressure 2 0.1 to 5% by mass, preferably 0.5 to 3% by mass.
The temperature of the heavy oil reservoir is 20-120 ℃, the pressure of the heavy oil reservoir is 5-50 MPa, and the viscosity of the heavy oil is 1000-50000 mPa.s.
In the chemical agent composition of the invention, phloroglucinol polymerThe ether has aromatic ring skeleton, ether bond and fatty chain, and can be accumulated pi-pi, hydrogen bond and hydrophobic association with asphalt and colloid in thick oil, so that the self association of asphalt and colloid is weakened, and the viscosity of thick oil is reduced; on the other hand, has a highly branched skeleton structure and ether bond to CO 2 Has good affinity and can improve CO 2 Solubility and dissolution efficiency in thick oil, reaching the aim of CO 2 The purpose of synergetic viscosity reduction. In addition, the auxiliary triazolyl ester has the function of reacting with CO 2 Compatible triazole ring and ester group, CO 2 Has good solubility. Chemical agent composition containing phloroglucinol polyether and triazole ester in CO 2 Has excellent solubility, and can be combined with CO in a wide temperature and pressure range 2 Synergistic viscosity reduction greatly improves the fluidity of thick oil. The composition does not contain low-flash organic solvent, has good safety, and is convenient to store, transport and inject. The chemical agent assisted thickened oil CO 2 Viscosity reduction and synergy method not only can improve CO of thick oil 2 Throughput efficiency, shortened throughput period, reduced thickened oil exploitation cost and improved oil displacement recovery ratio. Furthermore, the method can dissolve chemical agent in CO in liquid state or supercritical state 2 The chemical agent is neutral in electricity, low in concentration and low in adsorption loss.
The chemical agent composition and the thickened oil CO of the invention 2 The huff-puff viscosity-reducing synergistic method can be used for, but not limited to, a heavy oil reservoir with the stratum temperature of 20-120 ℃, the stratum pressure of 5-50 MPa and the crude oil viscosity of 1000-50000 mPa.s. At injection pressure of CO 2 0.1 to 5.0 percent of chemical agent composition is added to develop CO 2 And (3) carrying out high-pressure physical property experiments on the thick oil. The results show that, after the chemical agent composition of the present invention is added at 80℃and 12MPa, CO 2 The dissolved gas-oil ratio of the thickened oil is improved by more than 23 percent, and the maximum amplification reaches 40.59 percent. CO 2 The synergistic viscosity reduction rate with the chemical agent reaches more than 87 percent; up to 97.87% higher than pure CO 2 The viscosity reduction rate of (2) is improved by 30.57 percent.
Drawings
FIG. 1 is CO 2 High-temperature high-pressure physical property solid of thick oilAnd (5) checking a flow chart.
1 in fig. 1 is a plunger pump; 2 is a valve; 3 is a sample preparation kettle; 4 is a constant temperature system; 5 is a piston; 6 is a liquid storage bottle; 7 is a gas indicating bottle; 8 is a gas meter.
FIG. 2 is a flow chart of constant temperature and pressure transfer of live oil.
9 in fig. 2 is a plunger pump I;10 is a valve; 11 is a sample preparation kettle; 12 is a constant temperature system I;13 is an intermediate piston container; 14 is a plunger pump II;15 is a constant temperature system II.
FIG. 3 is a graph showing the relationship between the gas-oil ratio of heavy oil and the saturation pressure.
The thick oil is provided by victory oil field, the temperature of the oil reservoir is 80 ℃, and the pressure of the oil reservoir is 12MPa. CO is carried out at a temperature of 80 DEG C 2 The relation between the measured dissolved gas-oil ratio and the saturation pressure is shown in figure 3, and the relation between the gas-oil ratio and the saturation pressure is fitted by the graph: y= 5.4933x-17.067. The method is calculated by the relation: CO at formation pressure (12 MPa) 2 And the dissolved gas-oil ratio of the thick oil is 48.85m 3 /m 3 I.e. the thick oil can dissolve up to 48.85 times of the volume of CO under the formation condition 2 (standard state).
Detailed Description
The present invention will be further described with reference to specific examples in order to better understand the present invention and to better demonstrate the advantageous effects thereof. It is noted herein that the following examples are given solely for the purpose of further illustration of the present invention and are not to be construed as limiting the scope of the present invention, as many insubstantial modifications and variations of the invention will be within the scope of the invention as would be recognized by those skilled in the art in light of the present disclosure.
The raw materials used in the embodiments of the present invention are commercially available or custom made.
[ example 1 ]
(a) Preparation of phloroglucinol polyether:
126g of anhydrous phloroglucinol (1 mol), 5.6g of sodium hydroxide, was added to the autoclave, and the air in the flask was removed in vacuo. N (N) 2 Under protection, the system was heated to 120℃and 348g (6 m) of water were slowly introducedAnd (3) propylene oxide, wherein the control pressure is less than or equal to 0.20MPa. After the reaction is finished, the temperature is reduced to 90 ℃, the low-boiling-point substances are removed under reduced pressure, and after cooling, the reaction product is neutralized and dehydrated to obtain the phloroglucinol polyoxypropylene (6) ether (a) 1 +a 2 +a 3 ＝6，b 1 、b 2 、b 3 、c 1 、c 2 、c 3 All 0) 456.9g, yield 96.4%.
(b) Preparation of the triazole ester auxiliary agent:
(1) histidine methyl ester dihydrochloride (243 g,1 mol) was dissolved in 6M HCl (200 mL), cooled in an ice salt bath (-5-3deg.C), and stirred to give solution A. NaNO 2 (83 g,1.2 mol) was dissolved in 50mL of water and cooled in an ice bath to give solution B. Slowly dripping the solution B into the solution A, and keeping the system temperature at-5 to-3 ℃. After completion of the dropwise addition, the mixture was reacted for 5 minutes, and urea (7.2 g,0.12 mol) was added to quench excess NaNO 2 Diazo solution C is obtained.
(2) NaN is processed 3 (65 g,1 mol) and sodium acetate (33 g,0.4 mol) were dissolved in 200mL of water, and cooled in an ice bath to obtain solution D. The diazonium solution C is slowly dripped into the solution D, and the reaction is continued for 1 hour after the dripping is completed. Ethyl acetate extraction, organic phase with anhydrous Na 2 SO 4 And (5) drying. Filtration and concentration gave 182.3g of an azide compound in 93.5% yield.
(3) Ethyl 2-hexynoate (70 g,0.5 mol), the azide obtained in step (2) (97.5 g,0.5 mol), cuSO 4 ·5H 2 O (6.25 g,0.025 mol), na Ascorbate (9.9 g,0.05 mol) was dissolved in a 500mL reaction flask, and N was exchanged 2 Three times, N 2 Under the protection, 100mL of methanol and 100mL of water are added, and the mixture is stirred for 12 hours at normal temperature. Removing most of the solvent under reduced pressure, CH 2 Cl 2 Extraction of the organic phase with anhydrous Na 2 SO 4 And (5) drying. Filtration and concentration gave 159.8g of the corresponding triazolyl ester in 95.4% yield.
(c) The chemical agent composition containing phloroglucinol polyether and triazolyl ester is prepared by the following steps:
mixing the phloroglucinol polyoxypropylene (6) ether prepared in the step (a) and the triazole ester prepared in the step (b) in a molar ratio of 1:3 at normal temperature, and stirring for 3 hours to obtain the chemical agent composition S01 containing the phloroglucinol polyether.
[ example 2 ]
(a) Preparation of phloroglucinol polyether:
(1) 126g of anhydrous phloroglucinol (1 mol), 5.6g of sodium hydroxide, was added to the autoclave, and the air in the flask was removed in vacuo. N (N) 2 Under the protection, the system is heated to 110 ℃, 264g (6 mol) of ethylene oxide is slowly introduced, and the pressure is controlled to be less than or equal to 0.10MPa. After the reaction is finished, the temperature is reduced to 90 ℃, the low-boiling-point substances are removed under reduced pressure, and the phloroglucinol polyoxyethylene (6) ether (a) is obtained after neutralization and dehydration after cooling 1 +a 2 +a 3 ＝6，b 1 、b 2 、b 3 、c 1 、c 2 、c 3 All 0) 378.3g, yield 97.0%.
(2) To the dried reaction vessel were added 195g (0.5 mol) of phloroglucinol polyoxyethylene (6) ether, 102.4g (0.5 mol) of chlorododecane, 20.0g (0.5 mol) of sodium hydroxide, and oxygen was removed in vacuo. At N 2 Under the protection, 300mL of benzene is added, heated and refluxed for 8 hours. Washing with water, removing the solvent under reduced pressure, and drying to obtain 261.8g of phloroglucinol polyoxyethylene (6) lauryl ether with a yield of 93.8%.
(b) The chemical agent composition containing phloroglucinol polyether and triazolyl ester is prepared by the following steps:
mixing the phloroglucinol polyoxyethylene (6) lauryl ether prepared in the step (a) and the triazole ester prepared in the step (b) in a molar ratio of 1:4 at normal temperature, and stirring for 3 hours to obtain the chemical agent composition S02 containing the phloroglucinol polyether.
[ example 3 ]
(a) Preparation of phloroglucinol polyether:
126g of anhydrous phloroglucinol (1 mol), 6.0g of potassium hydroxide, and the air in the reaction flask was removed in vacuo. N (N) 2 Under the protection, the system is heated to 130 ℃, 432g (6 mol) of epoxybutane is slowly introduced, and the pressure is controlled to be less than or equal to 0.20MPa. After the reaction is finished, the temperature is reduced to 90 ℃, the low-boiling-point substances are removed under reduced pressure, and after cooling, the reaction product is neutralized and dehydrated to obtain the phloroglucinol polyoxybutylene (6) ether (a) 1 +a 2 +a 3 ＝6，b 1 、b 2 、b 3 、c 1 、c 2 、c 3 All 0) 537.9g, yield 96.4%.
(b) The chemical agent composition containing phloroglucinol polyether and triazolyl ester is prepared by the following steps:
mixing the phloroglucinol polyoxybutylene (6) ether prepared in the step (a) and the triazole ester prepared in the step (b) in a molar ratio of 1:5 at normal temperature, and stirring for 3 hours to obtain the chemical agent composition S03 containing the phloroglucinol polyether.
[ example 4 ]
(a) Preparation of phloroglucinol polyether:
126g of anhydrous phloroglucinol (1 mol), 6.0g of sodium hydroxide, was added to the autoclave, and the air in the flask was removed in vacuo. N (N) 2 Under the protection, the system is heated to 110 ℃, 132g (3 mol) of ethylene oxide is slowly introduced, and the pressure is controlled to be less than or equal to 0.10MPa. After the reaction of the ethylene oxide is finished, the temperature is raised to 120 ℃, 174g (3 mol) of propylene oxide is slowly introduced, and the pressure is controlled to be less than or equal to 0.20MPa. After the reaction is finished, the temperature is reduced to 90 ℃, the low-boiling-point substances are removed under reduced pressure, and after cooling, the reaction product is neutralized and dehydrated to obtain the phloroglucinol polyoxyethylene (3) polyoxypropylene (3) ether (a) 1 +a 2 +a 3 ＝3，b 1 +b 2 +b 3 ＝3，c 1 、c 2 、c 3 0) 413.9g, yield 95.8%.
(b) Preparation of the triazole ester auxiliary agent:
(1) l-tyrosine ethyl ester hydrochloride (245.7 g,1 mol) was dissolved in 6M HCl (200 mL), cooled in an ice salt bath (-5-3deg.C), and stirred to give solution A. NaNO 2 (83 g,1.2 mol) was dissolved in 50mL of water and cooled in an ice bath to give solution B. Slowly dripping the solution B into the solution A, and keeping the system temperature at-5 to-3 ℃. After completion of the dropwise addition, the mixture was reacted for 5 minutes, and urea (7.2 g,0.12 mol) was added to quench excess NaNO 2 Diazo solution C is obtained.
(2) NaN is processed 3 (65 g,1 mol) and sodium acetate (33 g,0.4 mol) were dissolved in 200mL of water, and cooled in an ice bath to obtain solution D. The diazonium solution C is slowly dripped into the solution D, and the reaction is continued for 1 hour after the dripping is completed. Ethyl acetate extraction, organic phase with anhydrous Na 2 SO 4 And (5) drying. FiltrationConcentration gave 110.8g of azide in 94.2% yield.
(3) Ethyl propiolate (49 g,0.5 mol), the azide from step (2) (97.5 g,0.5 mol), cuSO 4 ·5H 2 O (6.25 g,0.025 mol), na Ascorbate (9.9 g,0.05 mol) was dissolved in a 500mL reaction flask, and N was exchanged 2 Three times, N 2 Under the protection, 100mL of methanol and 100mL of water are added, and the mixture is stirred for 12 hours at normal temperature. Removing most of the solvent under reduced pressure, CH 2 Cl 2 Extraction of the organic phase with anhydrous Na 2 SO 4 And (5) drying. Filtration and concentration gave 138.9g of the corresponding triazolyl ester in 94.8% yield.
(c) The chemical agent composition containing phloroglucinol polyether and triazolyl ester is prepared by the following steps:
mixing the phloroglucinol polyoxyethylene (3) polyoxypropylene (3) ether prepared in the step (a) and the triazole ester prepared in the step (b) in a molar ratio of 1:6 at normal temperature, and stirring for 3 hours to obtain the chemical agent composition S04 containing the phloroglucinol polyether.
[ example 5 ]
(a) Preparation of phloroglucinol polyether:
126g of anhydrous phloroglucinol (1 mol), 6.0g of sodium hydroxide, was added to the autoclave, and the air in the flask was removed in vacuo. N (N) 2 Under the protection, the system is heated to 110 ℃, 132g (3 mol) of ethylene oxide is slowly introduced, and the pressure is controlled to be less than or equal to 0.10MPa. After the reaction of the ethylene oxide is finished, the temperature is raised to 120 ℃, 216g (3 mol) of butylene oxide is slowly introduced, and the pressure is controlled to be less than or equal to 0.20MPa. After the reaction is finished, the temperature is reduced to 90 ℃, the low-boiling-point substances are removed under reduced pressure, and after cooling, the reaction product is neutralized and dehydrated to obtain the phloroglucinol polyoxyethylene (3) polyoxybutylene (3) ether (a) 1 +a 2 +a 3 ＝3，b 1 +b 2 +b 3 ＝3，c 1 、c 2 、c 3 All 0) 455.04g, yield 96.0%.
(b) The chemical agent composition containing phloroglucinol polyether and triazolyl ester is prepared by the following steps:
mixing the phloroglucinol polyoxyethylene (3) polyoxybutylene (3) ether prepared in the step (a) and the triazole ester prepared in the step (b) in a molar ratio of 1:8 at normal temperature, and stirring for 3 hours to obtain the chemical agent composition S05 containing the phloroglucinol polyether.
[ example 6 ]
(a) Preparation of phloroglucinol polyether:
126g of anhydrous phloroglucinol (1 mol), 6.0g of sodium hydroxide, was added to the autoclave, and the air in the flask was removed in vacuo. N (N) 2 Under the protection, the system is heated to 120 ℃, 174g (3 mol) of propylene oxide is slowly introduced, and the pressure is controlled to be less than or equal to 0.20MPa. After the reaction of propylene oxide is finished, 216g (3 mol) of butylene oxide is slowly introduced, and the pressure is controlled to be less than or equal to 0.20MPa. After the reaction is finished, the temperature is reduced to 90 ℃, the low-boiling-point substances are removed under reduced pressure, and after cooling, the reaction product is neutralized and dehydrated to obtain the phloroglucinol polyoxypropylene (3) polyoxybutylene (3) ether (a) 1 +a 2 +a 3 ＝3，b 1 +b 2 +b 3 ＝3，c 1 、c 2 、c 3 All 0) 492.78g, the yield was 95.5%.
(b) The chemical agent composition containing phloroglucinol polyether and triazolyl ester is prepared by the following steps:
mixing the phloroglucinol polyoxypropylene (3) polyoxybutylene (3) ether prepared in the step (a) and the triazole ester prepared in the step (b) in the molar ratio of 1:8 in the example 4 at normal temperature, and stirring for 3 hours to obtain the chemical agent composition S06 containing the phloroglucinol polyether.
[ example 7 ]
(a) Preparation of phloroglucinol polyether:
(1) 126g of anhydrous phloroglucinol (1 mol), 6.0g of potassium hydroxide, and the air in the reaction flask was removed in vacuo. N (N) 2 Under the protection, the system is heated to 110 ℃, 396g (9 mol) of ethylene oxide is slowly introduced, and the pressure is controlled to be less than or equal to 0.10MPa. After the reaction is finished, the temperature is reduced to 90 ℃, the low-boiling-point substances are removed under reduced pressure, and the phloroglucinol polyoxyethylene (9) ether (a) is obtained after neutralization and dehydration after cooling 1 +a 2 +a 3 ＝9，b 1 、b 2 、b 3 、c 1 、c 2 、c 3 0) 504.3g each, yield 96.6%.
(2) 261g (0.5 mol) of phloroglucinol are introduced into a dry reaction vesselPolyoxyethylene (9) ether, 116.4g (0.5 mol) chlorotetradecane, 20.0g (0.5 mol) sodium hydroxide, and oxygen was removed in vacuo. At N 2 Under the protection, 300mL of toluene is added, heated and refluxed for 8 hours. Washing with water, removing the solvent under reduced pressure, and drying to obtain 334.7g of phloroglucinol polyoxyethylene (9) tetradecyl ether with a yield of 93.2%.
(b) Preparation of the triazole ester auxiliary agent:
(1) histidine methyl ester dihydrochloride (243 g,1 mol) was dissolved in 6M HCl (200 mL), cooled in an ice salt bath (-5-3deg.C), and stirred to give solution A. NaNO 2 (83 g,1.2 mol) was dissolved in 50mL of water and cooled in an ice bath to give solution B. Slowly dripping the solution B into the solution A, and keeping the system temperature at-5 to-3 ℃. After completion of the dropwise addition, the mixture was reacted for 5 minutes, and urea (7.2 g,0.12 mol) was added to quench excess NaNO 2 Diazo solution C is obtained.
(2) NaN is processed 3 (65 g,1 mol) and sodium acetate (33 g,0.4 mol) were dissolved in 200mL of water, and cooled in an ice bath to obtain solution D. The diazonium solution C is slowly dripped into the solution D, and the reaction is continued for 1 hour after the dripping is completed. Ethyl acetate extraction, organic phase with anhydrous Na 2 SO 4 And (5) drying. Filtration and concentration gave 182.3g of an azide compound in 93.5% yield.
(3) Ethyl propiolate (49.1 g,0.5 mol), the azide from step (2) (97.5 g,0.5 mol), cuSO 4 ·5H 2 O (6.25 g,0.025 mol), na Ascorbate (9.9 g,0.05 mol) was dissolved in a 500mL reaction flask, and N was exchanged 2 Three times, N 2 Under the protection, 100mL of methanol and 100mL of water are added, and the mixture is stirred for 12 hours at normal temperature. Removing most of the solvent under reduced pressure, CH 2 Cl 2 Extraction of the organic phase with anhydrous Na 2 SO 4 And (5) drying. Filtration and concentration gave 138.5g of the corresponding triazolyl ester in 94.5% yield.
(b) The chemical agent composition containing phloroglucinol polyether and triazolyl ester is prepared by the following steps:
and (3) mixing the phloroglucinol polyoxyethylene (9) tetradecyl ether prepared in the step (a) and the triazole ester prepared in the step (b) in a molar ratio of 1:12 at normal temperature, and stirring for 3 hours to obtain the chemical agent composition S07 containing the phloroglucinol polyether.
[ example 8 ]
(a) Preparation of phloroglucinol polyether:
126g of anhydrous phloroglucinol (1 mol), 6.0g of sodium hydroxide, was added to the autoclave, and the air in the flask was removed in vacuo. N (N) 2 Under the protection, the system is heated to 110 ℃, 264g (6 mol) of ethylene oxide is slowly introduced, and the pressure is controlled to be less than or equal to 0.10MPa. After the reaction of the ethylene oxide is finished, the temperature is raised to 120 ℃, 174g (3 mol) of propylene oxide is slowly introduced, and the pressure is controlled to be less than or equal to 0.20MPa. After the reaction is finished, the temperature is reduced to 90 ℃, the low-boiling-point substances are removed under reduced pressure, and after cooling, the reaction product is neutralized and dehydrated to obtain the phloroglucinol polyoxyethylene (6) polyoxypropylene (3) ether (a) 1 +a 2 +a 3 ＝3，b 1 +b 2 +b 3 ＝6，c 1 、c 2 、c 3 All 0) 543.1g, yield 96.3%.
(b) The chemical agent composition containing phloroglucinol polyether and triazolyl ester is prepared by the following steps:
mixing the phloroglucinol polyoxyethylene (6) polyoxypropylene (3) ether prepared in the step (a) and the triazole ester prepared in the step (b) in a molar ratio of 1:10 at normal temperature, and stirring for 3 hours to obtain the chemical agent composition S08 containing the phloroglucinol polyether.
[ example 9 ]
(a) Preparation of phloroglucinol polyether:
126g of anhydrous phloroglucinol (1 mol), 6.0g of sodium hydroxide, was added to the autoclave, and the air in the flask was removed in vacuo. N (N) 2 Under the protection, the system is heated to 110 ℃, 132g (3 mol) of ethylene oxide is slowly introduced, and the pressure is controlled to be less than or equal to 0.10MPa. After the reaction of the ethylene oxide is finished, the temperature is raised to 120 ℃, 174g (3 mol) of propylene oxide is slowly introduced, and the pressure is controlled to be less than or equal to 0.20MPa. After the reaction of propylene oxide is finished, 216g (3 mol) of butylene oxide is slowly introduced, and the pressure is controlled to be less than or equal to 0.20MPa. After the reaction is finished, the temperature is reduced to 90 ℃, the low-boiling-point substances are removed under reduced pressure, and after cooling, the reaction product is neutralized and dehydrated to obtain the phloroglucinol polyoxyethylene (3) polyoxypropylene (3) polyoxybutylene (3) ether (a) 1 +a 2 +a 3 ＝3，b 1 +b 2 +b 3 ＝3，c 1 +c 2 +c 3 =3) 607.8g, yield 93.8%.
(b) The chemical agent composition containing phloroglucinol polyether and triazolyl ester is prepared by the following steps:
mixing the phloroglucinol polyoxyethylene (3) polyoxypropylene (3) polyoxybutylene (3) ether prepared in the step (a) and the triazole ester prepared in the step (b) in the molar ratio of 1:16 in the example 7 at normal temperature, and stirring for 3 hours to obtain the chemical agent composition S09 containing the phloroglucinol polyether.
[ comparative example 1 ]
The phloroglucinol polyoxypropylene (6) ether and octylphenol polyoxypropylene (3) ether prepared in example 1 (preparation method same as that of example 3 of patent CN 202010619848.8) were mixed and stirred at a molar ratio of 1:3 for 3 hours at room temperature to obtain a chemical composition S10.
Comparative example 2 phloroglucinol polyoxypropylene (6) ether S11 prepared in example 1.
[ example 10 ] CO 2 And (3) measuring the gas-oil ratio and the saturation pressure of the thick oil.
The invention refers to the standard GB/T26981-2011, adopts the device of figure 1 to develop CO respectively 2 Thickened oil system and CO 2 High-pressure physical property experiment of thickened oil/chemical agent system to finish CO 2 And (3) measuring the gas-oil ratio and the saturation pressure of the thick oil. The saturation pressure is plotted on the abscissa, the gas-oil ratio is plotted on the ordinate, and a graph of the gas-oil ratio versus the saturation pressure is fitted to the graph. Calculating the CO under the formation pressure according to the relation of the fitting curve 2 Dissolved gas to oil ratio in heavy oil, i.e. how much CO is dissolved at maximum by the volume of formation oil at formation pressure 2 (standard state).
(a) High temperature and high pressure CO 2 Thickened oil dissolution experiment
Develop CO with certain gas-oil ratio 2 The thick oil dissolution experiment is that firstly, thick oil and CO needed by the experiment are calculated 2 The dosage is as follows. If chemical evaluation experiments are carried out, the required chemical dosage is calculated according to the chemical concentration. The specific experimental steps are as follows: 1. weighing a certain amount of dehydrated thick oil (and chemical agent) in a sample preparation kettle. 2. And (3) raising the sample preparation kettle to an experimental temperature, removing oxygen in the kettle, and closing a valve at the top of the piston. 3.Injecting a certain amount of CO into the sample preparation kettle 2 . 4. The plunger pump was connected to the sample preparation tank, and the constant pressure mode was set for the plunger pump, the pressure was set to be higher than the saturation pressure (estimated), and the stirring speed was set to be 30 minutes/time. 5. Along with CO 2 Dissolving in thick oil, and gradually reducing the volume of the sample preparation kettle. 6. And (3) finishing sample preparation when the volume of the plunger pump (or the sample preparation kettle) is not changed.
(b) Gas-oil ratio test
The experimental procedure was as follows: 1. waiting for step (a) CO 2 After the dissolution is completed, the pressure of the sample preparation kettle is increased by 2MPa. Slowly opening a valve of the sample preparation kettle to release a small amount of CO 2 And closing the valve until continuous live oil flows out. 2. Slowly discharging about 10mL of active oil to a liquid storage bottle with a piston under constant pressure. 3. The crude oil is remained in a liquid storage bottle after degassing, CO 2 After passing through the gas indicating bottle, the gas enters a gas meter. 4. The gauge gives the standard atmospheric pressure CO 2 Volume V g . 5. Weighing the mass of crude oil in the liquid storage bottle, and calculating to obtain the volume V of the crude oil o . The gas-oil ratio is V g /V o . The experiment was repeated three times to obtain an average gas-oil ratio.
(c) Saturation pressure test
CO with a certain oil-gas ratio at a certain temperature 2 In a thick oil liquid phase system, the pressure at which the first bubble occurs when the pressure drops is the bubble point pressure, also known as the saturation pressure. The saturation pressure has important significance for the field exploitation of the oil field. The saturation pressure is controlled by CO at constant temperature 2 The P-V relationship of the thickened oil system is obtained. The experimental steps are as follows: 1. waiting for step (a) CO 2 After the dissolution was completed, the pressure of the sample preparation vessel was increased by about 5MPa, and the stirring speed was adjusted to 1 minute/time. 2. After the system pressure and temperature are stable for 30 minutes, the liquid volume and pressure in the pump are read. 2. The system pressure is reduced by 2MPa, and the volume and pressure of the liquid in the pump are read after the system is stabilized for 5 minutes. 3. Repeating step 2, and at least three groups of experiments are completed above the saturation pressure, and the corresponding pressure and volume are read. 4. Until the pressure is near the saturation pressure point (the same pressure is reduced and the volume is increased), the plunger pump is changed into a constant-volume mode from a constant pressure mode, and the pressure in the kettle is read after the pressure is stabilized for 30 minutes. 5. Increasing constancyAfter the volume is stabilized for 5 minutes, the pressure in the sample preparation kettle and the volume of liquid in the pump are read. 6. Repeating step 5, and reading the corresponding pressure and volume after at least three experiments are completed below the saturation pressure. 6. The P-V relationship is obtained, and the inflection point of the curve is the bubble point pressure (saturation pressure).
The thick oil is provided by victory oil field, the temperature of the oil reservoir is 80 ℃, and the pressure of the oil reservoir is 12MPa. First, CO was developed at reservoir temperature (80 ℃ C.) 2 The relation between the measured dissolved gas-oil ratio and the saturation pressure is shown in figure 3, and the relation between the gas-oil ratio and the saturation pressure is fitted by the graph: y= 5.4933x-17.067. The method is calculated by the relation: CO at formation pressure (12 MPa) 2 And the dissolved gas-oil ratio of the thick oil is 48.85m 3 /m 3 I.e. the thick oil can dissolve up to 48.85 times of the volume of CO under the formation condition 2 (standard state).
Chemical agent composition containing phloroglucinol polyether with certain concentration is added, and CO is developed by the same method 2 And (3) obtaining a relation curve of the dissolved gas-oil ratio and the saturation pressure through a high-pressure physical experiment of the thickened oil/chemical agent. And obtaining the gas-oil ratio under the oil reservoir condition (80 ℃ and 12 MPa) by fitting the curve relation, and calculating the increase amplitude of the gas-oil ratio after the chemical agent is added. The results are shown in Table 1.
TABLE 1 chemical agent composition vs. CO 2 Influence of gas-oil ratio of thickened oil
Example 11 live oil viscometry
A live oil sample was prepared according to the gas-oil ratio at formation pressure obtained in example 10. Experimental procedure is the same as in example 10, step (a). The following is the viscosity test procedure. 1. Waiting for step (a) CO 2 After the dissolution is completed, the stirring is stopped, and an outlet valve of the sample preparation kettle is arranged at the upper end and is kept stand for 1 hour. 2. The pressure of the sample preparation kettle is increased by 2MPa, and the sample preparation kettle is connected with an intermediate piston container. 3. Above saturation pressure, the live oil is transferred at constant pressure. 4. Filling N in a high-pressure sealing unit of a Hakke rheometer 2 The pressure of the closed unit is enabled to reach the formation pressure (12 MPa), and the temperature reaches the formation temperature (80 ℃). 5. The middle piston container is connected with the closed unit, and the active oil is transferred at constant pressure. 6. Standing at constant temperature and pressure for 5min at 100s -1 And (5) completing the viscosity degree test of the active oil at the shear rate.
First, the viscosity of the thickened oil was measured under formation conditions (80 ℃,12 MPa) and was 15548.6mpa.s. Then, under the formation conditions, CO was measured 2 The viscosity of the thickened oil system was 5084.4mPa.s. Under formation conditions, CO 2 The viscosity reduction rate of the thickened oil is 67.3 percent. Finally, CO determination under formation conditions 2 Viscosity of the thickened oil/chemical agent system, and the viscosity reduction rate was calculated. The test results are shown in Table 2.
TABLE 2 chemical agent/CO 2 Viscosity reducing effect on thickened oil
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Claims (14)
1. A chemical agent composition containing phloroglucinol polyether comprises phloroglucinol polyether and triazole ester,
wherein the phloroglucinol polyether is at least one of structures shown in a formula (I):
in the formula (I), R 1 、R 2 、R 3 Independently selected from (CH) 2 ) j H, j is any integer from 0 to 4; a, a 1 、a 2 、a 3 Is substituted by R 1 The number of polyether groups b 1 、b 2 、b 3 Is substituted by R 2 The number of polyether groups c 1 、c 2 、c 3 Is substituted by R 3 The number of polyether groups; a, a 1 、a 2 、a 3 、b 1 、b 2 、b 3 、c 1 、c 2 、c 3 Independently is any integer from 0 to 50, and a 1+ a 2+ a 3+ b 1+ b 2+ b 3+ c 1+ c 2+ c 3 >0；X 1 、X 2 、X 3 Independently selected from hydrogen atoms, C 1 ～C 50 Is a hydrocarbon group or a substituted hydrocarbon group;
the triazole ester is at least one selected from structures shown in a formula (II):
in the formula (II), R 4 、R 5 、R 6 Independently is a hydrogen atom, C 1 ～C 50 Is a hydrocarbon group or a substituted hydrocarbon group; y is Y 1 、Y 2 、Y 3 Independently a hydrogen atom or COOR 7 And not simultaneously being hydrogen atoms, R 7 Is C 1 ～C 50 Is a hydrocarbon group or a substituted hydrocarbon group; n is n 1 、n 2 、n 3 Independently is any integer from 0 to 20.
2. The chemical agent composition according to claim 1, wherein:
the R is 1 、R 2 、R 3 Independently selected from (CH) 2 ) j H, j is any integer from 0 to 4, and R 1 、R 2 、R 3 Not both hydrogen atoms; a, a 1 、a 2 、a 3 、b 1 、b 2 、b 3 、c 1 、c 2 、c 3 Independently is any integer from 0 to 50, and a 1+ a 2+ a 3+ b 1+ b 2+ b 3+ c 1+ c 2+ c 3 >0；X 1 、X 2 、X 3 Independently selected from hydrogen atoms, C 1 ～C 50 Is a hydrocarbon group or a substituted hydrocarbon group;
R 4 、R 5 、R 6 independently is a hydrogen atom, C 1 ～C 50 Is a hydrocarbon group or a substituted hydrocarbon group; y is Y 1 、Y 2 、Y 3 Independently a hydrogen atom or COOR 7 And not simultaneously being hydrogen atoms, R 7 Is C 1 -a C50 hydrocarbyl or substituted hydrocarbyl group; n is n 1 、n 2 、n 3 Independently is any integer from 0 to 20.
3. The chemical agent composition according to claim 1, wherein:
the R is 1 、R 2 、R 3 Independently selected from (CH) 2 ) j H, j is any integer from 0 to 4, and R 1 、R 2 、R 3 Comprising at least two different groups; a, a 1 、a 2 、a 3 、b 1 、b 2 、b 3 、c 1 、c 2 、c 3 Independently is any integer from 0 to 50, and a 1+ a 2+ a 3 >0，b 1+ b 2+ b 3 >0，c 1+ c 2+ c 3 >0；X 1 、X 2 、X 3 Independently selected from hydrogen atoms, C 1 ～C 50 Is a hydrocarbon group or a substituted hydrocarbon group;
R 4 、R 5 、R 6 independently is a hydrogen atom, C 1 ～C 50 Is a hydrocarbon group or a substituted hydrocarbon group; y is Y 1 、Y 2 、Y 3 Independently a hydrogen atom or COOR 7 And not simultaneously being hydrogen atoms, R 7 Is C 1 -a C50 hydrocarbyl or substituted hydrocarbyl group; n is n 1 、n 2 、n 3 Independently is any integer from 0 to 20.
4. The chemical agent composition according to claim 1, wherein:
the R is 1 、R 2 、R 3 Independently selected from (CH) 2 ) j H, j is any integer from 1 to 4; a, a 1 、a 2 、a 3 、b 1 、b 2 、b 3 、c 1 、c 2 、c 3 Independently is any integer from 0 to 40, and a 1+ a 2+ a 3 >0，b 1+ b 2+ b 3 >0，c 1+ c 2+ c 3 >0；X 1 、X 2 、X 3 Independently selected from hydrogen atoms, C 1 ～C 40 Is a hydrocarbon group or a substituted hydrocarbon group;
R 4 、R 5 、R 6 independently is a hydrogen atom, C 1 ～C 30 Is a hydrocarbon group or a substituted hydrocarbon group; y is Y 1 、Y 2 、Y 3 Independently a hydrogen atom or COOR 7 And not simultaneously being hydrogen atoms, R 7 Is C 1 ～C 30 Is a hydrocarbon group or a substituted hydrocarbon group; n is n 1 、n 2 、n 3 Independently is any integer from 0 to 10.
5. The chemical agent composition as claimed in claim 4, wherein:
the R is 1 、R 2 、R 3 Independently selected from (CH) 2 ) j H, j is any integer from 1 to 3; a, a 1 、a 2 、a 3 、b 1 、b 2 、b 3 、c 1 、c 2 、c 3 Independently is any integer from 0 to 30, and a 1+ a 2+ a 3 >0，b 1+ b 2+ b 3 >0，c 1+ c 2+ c 3 >0；X 1 、X 2 、X 3 Independently selected from hydrogen atoms, C 5 ～C 30 Is a hydrocarbon group or a substituted hydrocarbon group;
R 4 、R 5 、R 6 independently is a hydrogen atom, C 1 ～C 30 Is a hydrocarbon group or a substituted hydrocarbon group; y is Y 1 、Y 2 、Y 3 Independently a hydrogen atom or COOR 7 And not simultaneously being hydrogen atoms, R 7 Is C 1 ～C 30 Is a hydrocarbon group or a substituted hydrocarbon group; n is n 1 、n 2 、n 3 Independently is any integer from 0 to 10.
6. The chemical agent composition as claimed in claim 5, wherein:
the R is 1 、R 2 、R 3 Independently selected from (CH) 2 ) j H, j is any integer from 1 to 3, and R 1 、R 2 、R 3 Comprising at least two different groups; a, a 1 、a 2 、a 3 、b 1 、b 2 、b 3 、c 1 、c 2 、c 3 Independently is any integer from 0 to 30, and a 1+ a 2+ a 3 >0，b 1+ b 2+ b 3 >0，c 1+ c 2+ c 3 >0；X 1 、X 2 、X 3 Independently selected from hydrogen atoms, C 5 ～C 30 Is a hydrocarbon group or a substituted hydrocarbon group;
R 4 、R 5 、R 6 independently is a hydrogen atom, C 1 ～C 30 Is a hydrocarbon group or a substituted hydrocarbon group; y is Y 1 、Y 2 、Y 3 Independently a hydrogen atom or COOR 7 And not simultaneously being hydrogen atoms, R 7 Is C 1 ～C 30 Is a hydrocarbon group or a substituted hydrocarbon group; n is n 1 、n 2 、n 3 Independently is any integer from 0 to 10.
7. The chemical agent composition according to claim 1, wherein:
the molar ratio of the phloroglucinol polyether to the triazole ester is 1: (0.01 to 20), preferably 1: (0.05-10).
8. A process for preparing a chemical composition according to any one of claims 1 to 7 comprising mixing the phloroglucinol polyether with a triazole ester.
9. The preparation method of claim 8, wherein the phloroglucinol polyether is prepared by the steps of:
(1) under the action of alkali A, phloroglucinol reacts with epoxy compound to obtain X 1 、X 2 、X 3 Are all hydrogenAn atomic phloroglucinol polyether compound;
optionally, (2) reacting a phloroglucinol polyether compound with R in the presence of a base B 8 Cl reaction to obtain the phloroglucinol polyether; wherein R is 8 Is C 1 ～C 50 Or a substituted hydrocarbon group.
10. The method of manufacturing according to claim 9, wherein:
in the step (1), the reaction temperature is 100-140 ℃, the alkali A is at least one of sodium carbonate, sodium hydroxide and potassium hydroxide, and the dosage of the alkali A is 0.5-5.0% of the mass of the phloroglucinol; and/or the number of the groups of groups,
in the step (2), the reaction solvent is benzene or toluene, the alkali B is at least one of sodium hydroxide and potassium hydroxide, and the molar ratio of the alkali B to the phloroglucinol polyether compound is preferably 1.0-2.0.
11. The preparation method of claim 8, wherein the triazole ester is prepared by the following steps:
(1) ' amino compound or amino ester compound and NaNO in hydrochloric acid solution 2 Reacting to obtain diazonium salt;
(2) ' diazonium salt with NaN in weak base solution 3 Reacting to generate an azide;
(3) the' alkynyl ester compound reacts with the azide compound in the presence of a copper catalyst and a reducing agent to obtain the triazole ester.
12. The method of manufacturing according to claim 11, wherein:
in the step (1)' the reaction temperature is-8 to-3 ℃; the concentration of the hydrochloric acid solution is 2-6 mol/L; naNO 2 The molar ratio of the amino acid to the amino compound or the amino ester compound is 1 to 1.2; adding urea to quench after the reaction is finished, wherein the molar ratio of the urea to the amino compound or the amino ester compound is 0.1-0.12;
in the step (2)' the reaction temperature is-5 to 0 ℃; the weak base solution is at least one selected from sodium acetate, sodium propionate or sodium butyrate aqueous solution, and is weakThe concentration of the alkali solution is preferably 1.5-2.5 mol/L; naN (NaN) 3 The molar ratio of the amino acid to the amino compound or the amino ester compound is 1 to 1.2;
in the step (3)' the reaction temperature is normal temperature; the copper catalyst is selected from CuI, cuBr, cuSO 4 ·5H 2 At least one of O, wherein the molar ratio of the copper catalyst to the alkynyl ester compound is 0.05-0.1; the reducing agent is sodium ascorbate, and the molar ratio of the reducing agent to the alkynyl ester compound is 0.1-0.2; the molar ratio of the alkynyl ester compound to the azide compound is 0.8-1.2.
13. Thickened oil CO 2 A process for increasing the efficiency of throughput viscosity reduction comprising dissolving a chemical composition comprising a phloroglucinol polyether as defined in any one of claims 1 to 7 in liquid and/or supercritical CO 2 Is injected into the formation together.
14. Thickened oil CO according to claim 13 2 The method for reducing the viscosity and enhancing the efficiency of the huff and puff is characterized by comprising the following steps of:
the dosage of the chemical agent composition is CO under the injection pressure 2 0.1 to 5% by mass, preferably 0.5 to 3%; and/or the number of the groups of groups,
the temperature of the heavy oil reservoir is 20-120 ℃, the pressure of the heavy oil reservoir is 5-50 MPa, and the viscosity of the heavy oil is 1000-50000 mPa.s.
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