CN106590568A - Foam scrubbing agent composition with mineralization resistance for gas recovery by water drainage as well as preparation method and application thereof - Google Patents
Foam scrubbing agent composition with mineralization resistance for gas recovery by water drainage as well as preparation method and application thereof Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000006260 foam Substances 0.000 title claims abstract description 54
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 48
- 239000000203 mixture Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 238000011084 recovery Methods 0.000 title abstract description 8
- 238000005201 scrubbing Methods 0.000 title abstract description 4
- 230000033558 biomineral tissue development Effects 0.000 title abstract 3
- 239000007789 gas Substances 0.000 claims abstract description 59
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 34
- -1 nitrogen containing compound Chemical class 0.000 claims abstract description 34
- 229920000570 polyether Polymers 0.000 claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 claims abstract description 23
- 150000008052 alkyl sulfonates Chemical class 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims description 43
- 238000007599 discharging Methods 0.000 claims description 34
- 238000003786 synthesis reaction Methods 0.000 claims description 23
- 238000005086 pumping Methods 0.000 claims description 21
- 230000015572 biosynthetic process Effects 0.000 claims description 19
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 13
- 238000012545 processing Methods 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 2
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 229940126062 Compound A Drugs 0.000 claims 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims 1
- 239000008398 formation water Substances 0.000 claims 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 238000005187 foaming Methods 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 5
- 239000000654 additive Substances 0.000 abstract 2
- 230000000996 additive effect Effects 0.000 abstract 2
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 abstract 1
- 125000002947 alkylene group Chemical group 0.000 abstract 1
- 125000000547 substituted alkyl group Chemical group 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 40
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- 238000010992 reflux Methods 0.000 description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 20
- 239000004088 foaming agent Substances 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 18
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 18
- 238000009835 boiling Methods 0.000 description 18
- 238000001816 cooling Methods 0.000 description 17
- 238000005406 washing Methods 0.000 description 17
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 13
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 11
- 235000002639 sodium chloride Nutrition 0.000 description 11
- 239000012467 final product Substances 0.000 description 10
- JECYNCQXXKQDJN-UHFFFAOYSA-N 2-(2-methylhexan-2-yloxymethyl)oxirane Chemical compound CCCCC(C)(C)OCC1CO1 JECYNCQXXKQDJN-UHFFFAOYSA-N 0.000 description 9
- 230000018044 dehydration Effects 0.000 description 9
- 238000006297 dehydration reaction Methods 0.000 description 9
- 238000006073 displacement reaction Methods 0.000 description 9
- 238000000605 extraction Methods 0.000 description 9
- 238000004128 high performance liquid chromatography Methods 0.000 description 9
- 238000006386 neutralization reaction Methods 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000003208 petroleum Substances 0.000 description 9
- 239000001294 propane Substances 0.000 description 9
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 9
- 239000000376 reactant Substances 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000013517 stratification Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 238000005292 vacuum distillation Methods 0.000 description 9
- 238000001291 vacuum drying Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 239000013067 intermediate product Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 150000002028 dodecanols Chemical class 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- LDMOEFOXLIZJOW-UHFFFAOYSA-N 1-dodecanesulfonic acid Chemical compound CCCCCCCCCCCCS(O)(=O)=O LDMOEFOXLIZJOW-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- CACRRXGTWZXOAU-UHFFFAOYSA-N octadecane-1-sulfonic acid Chemical class CCCCCCCCCCCCCCCCCCS(O)(=O)=O CACRRXGTWZXOAU-UHFFFAOYSA-N 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- MYOWBHNETUSQPA-UHFFFAOYSA-N tetradecane-1-sulfonic acid Chemical compound CCCCCCCCCCCCCCS(O)(=O)=O MYOWBHNETUSQPA-UHFFFAOYSA-N 0.000 description 2
- KVGOXGQSTGQXDD-UHFFFAOYSA-N 1-decane-sulfonic-acid Chemical compound CCCCCCCCCCS(O)(=O)=O KVGOXGQSTGQXDD-UHFFFAOYSA-N 0.000 description 1
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical class CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 description 1
- JOONSONEBWTBLT-UHFFFAOYSA-N 2-tetradecylphenol Chemical compound CCCCCCCCCCCCCCC1=CC=CC=C1O JOONSONEBWTBLT-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- GCQVNVAYGOFTCL-UHFFFAOYSA-N CCCCCCCCCCCCCC[Na] Chemical compound CCCCCCCCCCCCCC[Na] GCQVNVAYGOFTCL-UHFFFAOYSA-N 0.000 description 1
- BRDJPCFGLMKJRU-UHFFFAOYSA-N DDAO Chemical compound ClC1=C(O)C(Cl)=C2C(C)(C)C3=CC(=O)C=CC3=NC2=C1 BRDJPCFGLMKJRU-UHFFFAOYSA-N 0.000 description 1
- 241000521257 Hydrops Species 0.000 description 1
- 206010030113 Oedema Diseases 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000006265 aqueous foam Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000003876 biosurfactant Substances 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003672 gas field water Substances 0.000 description 1
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical class CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 1
- SSILHZFTFWOUJR-UHFFFAOYSA-M hexadecane-1-sulfonate Chemical compound CCCCCCCCCCCCCCCCS([O-])(=O)=O SSILHZFTFWOUJR-UHFFFAOYSA-M 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 235000020681 well water Nutrition 0.000 description 1
- 239000002349 well water Substances 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
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/584—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 surfactants
-
- 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
Landscapes
- 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)
- Polyethers (AREA)
Abstract
The invention relates to a foam scrubbing agent composition with mineralization resistance for gas recovery by water drainage as well as a preparation method and application thereof. The composition mainly solves the problems of gas producing well production reduction and even unflowing due to excess effusion in exploitation process of gas producing wells in the prior art. The composition comprises the following components according to mol fraction: (1) 1 part of a long-chain polyether nitrogen containing compound; (2) 0.5-20 parts of alkyl sulfonate; wherein the long-chain polyether nitrogen containing compound comprises a molecular general formula shown in a formula (I), and R1 is C8-C30 fatty group; y is PO chain segment additive number; z is EO chain segment additive number; R2 is C1-C4 alkylene; R3 and R4 are selected from any one of C1-C5 alkyl and substituted alkyl. The technical scheme can better solve the problems. The foam scrubbing agent composition with mineralization resistance for gas recovery by water drainage has foaming height which is higher than 200mm, liquor carrying amount is higher than 140mL, and the composition can be applied to gas recovery by water drainage in high-salt gas field.
Description
Technical field
The present invention relates to a kind of resistance to salinity water pumping gas production foam discharging agent composition and preparation method and application, belongs to oil
Gas field chemical agent technical field.
Background technology
With the reinforcement of gas-field exploitation dynamics, the key issue that gas field water outlet is normally produced into restriction gas well.Foaming water discharge
Gas production is a kind of drainage gas recovery that recent domestic is developed rapidly, with equipment is simple, easy construction, low cost,
Applicable well depth scope is big, the advantages of do not affect gas well normally to produce.So-called foaming water discharge is exactly by the mineralized water of shaft bottom
Introduce some surfactants with specific function so as to during gas-liquid two-phase mixing perpendicular flow, produce a large amount of
Low-density resistance aqueous foam, foam takes water with air-flow from shaft bottom to ground, improves gas-liquid and vertically lifts liquid energy power, reaches draining and adopts
The purpose of gas.When gas field temperature and salinity are raised, the foamability and stability of foam discharging agent are all greatly reduced, usually
The effect of water pumping gas production is not reached.Therefore need exploitation that there is resisting high temperature, high salt, the foam discharging agent of height foaming efficiency.
At present water pumping gas production foaming agent adopts Recompounded multielement system mostly, at the same comprising nonionic surface active agent and from
Subtype surfactant.In order to strengthen the stability of single foam, alkali, alcohol, polymer, alkane are generally additionally added in formula
The auxiliary agents such as alkylolamides form strengthening foam.Patent CN102212344A discloses a kind of high-temperature foam scrubbing agent for drainage gas recovery,
Its component is by mass fraction：10～15 parts of lauryl sodium sulfate, 2～5 parts of APG, AES15～18 part, ten
20～25 parts of dialkyl sulfonates, 5～10 parts of biosurfactant, 27～48 parts of water, its salt resistant character is poor.Specially
Sharp CN102212348A discloses a kind of salt tolerant, methanol tolerance foam discharging agent, and individual component content by weight percentage is：Cocounut oil
Amido propyl betaine 20～40%, amine oxide 45～65%, alpha-alkene sulfonate 5～20%, triethanolamine 5～15%,
Fluorocarbon surfactant 0.2～2%, methyl alcohol 0～5%, can be resistant to salinity up to 180,000, but the agent contains fluorocarbon surface
Activating agent, not only cost greatly improve and have greater environmental impacts.
The content of the invention
One of the technical problem to be solved is that on stream hydrops is excessive for existing gas well, causes gas well to subtract
Produce the problem of even stop-spraying, there is provided a kind of gas well foam discharging agent composition for efficiently taking liquid, with good salt resistant character, rise
Bubble performance and fluid-carrying capability.
The two of the technical problem to be solved arrange to provide a kind of resistance to salinity for solving one of above-mentioned technical problem
The hydromining gas preparation method of foam discharging agent composition.
The three of the technical problem to be solved arrange to provide a kind of resistance to salinity for solving one of above-mentioned technical problem
The hydromining gas application process of foam discharging agent composition.
To solve one of above-mentioned technical problem, the technical solution used in the present invention is as follows：A kind of resistance to salinity water pumping gas production is used
Foam discharging agent composition includes following components with molar fraction：
(1) 1 part of long-chain polyether nitrogen-containing compound；
(2) 0.5～20 parts of alkylsulfonate；
Described long-chain polyether nitrogen-containing compound has following general molecular formula：
Formula (I)
Wherein, R1For C8～C30Fat-based；Y adds sum, y=0～20 for PO segments；Z adds sum for EO segments,
Z=0～60；R2For C1～C4Alkylidene；R3、R4For C1～C5Alkyl, replace alkyl in any one.
In above-mentioned technical proposal, the R1For C8～C30Fat-based, acyl group, carbonyl, ether, hydroxyl can be contained
Can be saturated carbon chains Deng group, it is also possible to containing unsaturated carbon chains, as preferred R1Preferred version be C10～C20
Alkyl, alkylbenzene.
In above-mentioned technical proposal, the R2Preferably C2H4Or C3H6, more preferably C2H4。
In above-mentioned technical proposal, the R3、R4For C1～C5Alkyl, replace alkyl in any one；Wherein institute
State and replace the substituent in alkyl to be the substituted radicals such as hydroxyl substituent, halogenic substituent.
In above-mentioned technical proposal, the preferred version of the z is more than 0, more preferably less than equal to 30, further preferably
For z=1～20.
In above-mentioned technical proposal, the preferred version of the y is more preferably y=1～20 more than 0.
In above-mentioned technical proposal, the alkylsulfonate preferably has following general molecular formula：
[R5SO3] jM, formula (II)；
R in formula5For C5～C30Alkyl, to make molecule shown in formula (II) in electroneutral cation, j is M's to M
Number, the value of j is the inverse of M valence state values；M can be various common cations, such as various metal cations,
Those skilled in the art can arbitrarily select.
In above-mentioned technical proposal, when M is preferably+1 valency, there is the alkylsulfonate molecule shown in formula (III) to lead to
Formula：
R5SO3M, formula (III)；
M preferably is selected from any one metal ion or ammonium ion in alkali metal；Further preferably：M preferred versions are
Any one metal ion in alkali metal, more preferably sodium or potassium ion, more preferably scheme are selected from sodium ion；
R5Preferred version is selected from C8～C22Alkyl, more preferably scheme is selected from C10～C18Alkyl.
In above-mentioned technical proposal, long-chain polyether nitrogen-containing compound is 1 with the mol ratio of alkylsulfonate:(0.2～10).
Foaming agent combination in the present invention does not have particular/special requirement when preparing to water, can be deionized water, can be with
It is the water containing inorganic mineral, and the water for containing inorganic mineral can be running water, gas well stratum water or gas well injection water.
To solve the two of above-mentioned technical problem, the technical solution used in the present invention is as follows：Resistance to salinity water pumping gas production is arranged with bubble
The preparation method of agent composition, comprises the following steps：
(1) synthesis of long-chain polyether nitrogen-containing compound
A, in the presence of base catalyst, R1OH obtains R with aequum propylene oxide reaction1O(CHCH3CH2O)yH；
B, in the presence of base catalyst, R1O(CHCH3CH2O)yH is obtained with aequum reacting ethylene oxide
R1O(CHCH3CH2O)y(CH2CH2O)z+1H；
C, by R1O(CHCH3CH2O)y(CH2CH2O)z+1H reacts Jing after processing with thionyl chloride and obtains
R1O(CHCH3CH2O)y(CH2CH2O)zR2Cl；
D, by R1O(CHCH3CH2O)y(CH2CH2O)z R2Cl and NR3R4In a solvent, reaction temperature 70～
90 DEG C of reactions obtain R Jing after processing1O(CHCH3CH2O)y(CH2CH2O)z R2NR3R4；
E, by R1O(CHCH3CH2O)y(CH2CH2O)z R2NR3R4With hydrogen peroxide in 60～70 DEG C of reactions, Jing process
After obtain long-chain polyether nitrogen-containing compound；
(2) preparation of foam discharging agent composition
The desired amount of long-chain polyether nitrogen-containing compound, alkylsulfonate are well mixed into obtain resistance to salinity water pumping gas production bubble row
Agent composition.
The key active ingredient of foam discharging agent of the present invention is alkylsulfonate and long-chain polyether nitrogen-containing compound, people in the art
Member knows, for the ease of transport and store or onsite application etc. from the aspect of, various supply forms can be adopted, for example not
Aqueous solid-state form, or aqueous solid-state form, or aqueous cream form, or aqueous solution form；It is water-soluble
Liquid form includes being made into the form of concentrate with water, is directly made into the foam discharging agent form of live desired concn；Wherein, to water
Can be deionized water without particular/special requirement, can also be the water containing inorganic mineral, and the water for containing inorganic mineral can
Be running water, gas well stratum water or gas well injection water.
In order to solve the three of technical problem, the technical solution used in the present invention is：The arbitrary described resistance to ore deposit of above-mentioned technical proposal
The change degree water pumping gas production application of foam discharging agent composition.
In above-mentioned technical proposal, the application, those skilled in the art can be according to related process of the prior art by institute
In the resistance to salinity water pumping gas production foam discharging agent composition application stated and gas well water pumping gas production, the stratum water of gas well is preferably suitable for
Salinity is 0～250000mg/L.
In the long-chain polyether nitrogen-containing compound of the resistance to salinity water pumping gas production foam discharging agent of the present invention comprising EO, PO etc. it is non-from
Sub-piece, can dramatically increase the salt resistant character of foam discharging agent, while it is a kind of amine oxide, be affected less by pH value,
Into nonionic surfactant under neutral or alkalescence, cationic is shown under acid condition, be a kind of multifunction surface activity
Agent, with stronger foam enhancing foam stability energy, has synergy well with anion surfactant；Alkylsulfonate has good
Good foaming capacity, and have preferable salt-resistance, both form compounding synergy after mixing, strengthen foam takes liquid energy
Power and foam stability energy.
The foam discharging agent composition of the present invention is applicable to gas well of the salinity less than 250000mg/L.According to SY/T
6465-2000《Foam drainage gas recovery foaming agent evaluation method》Foaming properties test is carried out to the foam discharging agent, foaming is high
Degree is more than 200mm, and liquid carry over is more than 140mL, with good frothing capacity, foam stability and fluid-carrying capability,
Achieve preferable technique effect.
In order to be better understood from the present invention, present disclosure is expanded on further with reference to embodiments, but the present invention's is interior
Appearance is not limited solely to the following examples.
Specific embodiment
【Embodiment 1】
The preparation of composition CX-1, preparation process：
(1) long-chain polyether nitrogen-containing compound (C12H25O(CHCH3CH2O)3(CH2CH2O)7CH2CH2N(CH3)2O)
Synthesis with prepare：
186.0 grams of dodecanols, 5.6 grams of potassium hydroxide are added in the pressure reactor equipped with agitating device, is heated to
When 80～90 DEG C, vacuum system is opened, be dehydrated under a high vacuum 1 hour, then with nitrogen displacement 3～4 times, by body
It is that reaction temperature is adjusted to 150 DEG C and is slowly passed through 179.9 grams of expoxy propane, control pressure≤0.60MPa is cooled to 90 DEG C,
Low-boiling-point substance is removed in vacuum, system reaction temperature is adjusted to 150 DEG C and is slowly passed through 360.0 grams of oxirane, control pressure by continuation
Power≤0.60MPa.After reaction terminates, neutralization, dehydration, obtain C after cooling12H25O(CHCH3CH2O)3(CH2CH2O)8
H, yield 98.8wt%.
339 are added in the four round flask equipped with reflux condensate device, thermometer, agitator and gas absorbing device
Gram C12H25O(CHCH3CH2O)3(CH2CH2O)8H and 57 gram of pyridine, is heated to 70 DEG C under stirring, use dropping funel
85 grams of thionyl chlorides are slowly added dropwise, are reacted 10 hours at 90 DEG C after completion of dropping.After reaction terminates, reactant is stood,
Cooling layering, neutrality is neutralized to sodium hydroxide solution by upper strata, with saturated common salt water washing 5-6 time of heat, after drying
Obtain intermediate product C12H25O(CHCH3CH2O)3(CH2CH2O)7CH2CH2Cl, yield is 88%.
By C12H25O(CHCH3CH2O)3(CH2CH2O)7CH2CH2143 grams of Cl add with reflux condensate device,
In thermometer, the four-hole boiling flask of agitator, 77 DEG C are heated to, by N (CH3)2Solution dropping funel slowly drips to flask
In, system remains alkalescent, stratification after reacting 10 hours.By the saturation food after the vacuum distillation of upper strata with heat
Salt water washing 5-6 time, obtains desired intermediate C12H25O(CHCH3CH2O)3(CH2CH2O)7
CH2CH2N(CH3)2, yield is 83%.
By C12H25O(CHCH3CH2O)3(CH2CH2O)7CH2CH2N(CH3)2100 grams are added to returned cold
In solidifying device, thermometer, the four-hole boiling flask of agitator, 60 DEG C are heated to, are slowly added dropwise H2O230 grams of solution,
React 5 hours at 70 DEG C, with petroleum ether extraction, vacuum drying, analyze by high performance liquid chromatography (HPLC), produce
C in thing12H25O(CHCH3CH2O)3(CH2CH2O)7CH2CH2N(CH3)2O content is 97.72wt%.
(2) preparation of foaming agent combination：
At normal temperatures and pressures, 70 grams of long-chain polyether nitrogen-containing compound obtained by synthesis is weighed in previous step in reactor,
Add appropriate local originally water dissolves；50.4 grams of dodecyl sodium sulfates are added thereto to again, add enough sheets
Ground running water is configured to the solution of 30wt% to 401 grams, is sufficiently stirred for 30min to being completely dissolved, obtains final product bubble
Foam agent composition CX-1.
【Embodiment 2】
The preparation of composition CX-2, preparation process：
(1) long-chain polyether nitrogen-containing compound (C16H33O(CHCH3CH2O)10(CH2CH2O)20CH2CH2
N(C2H5)(C3H7O) O) synthesis with prepare：
121 grams of hexadecanols, 3 grams of potassium hydroxide are added in the pressure reactor equipped with agitating device, it is heated to 80～
When 90 DEG C, vacuum system is opened, be dehydrated under a high vacuum 1 hour, it is then with nitrogen displacement 3～4 times, system is anti-
Answer temperature to be adjusted to 150 DEG C and be slowly passed through 300 grams of expoxy propane, control pressure≤0.60MPa is cooled to 90 DEG C, vacuum
Low-boiling-point substance is removed, system reaction temperature is adjusted to 150 DEG C and is slowly passed through 500.0 grams of oxirane, control pressure by continuation
≤0.60MPa.After reaction terminates, neutralization, dehydration, obtain C after cooling16H33O(CHCH3CH2O)10(CH2CH2O)21H,
Yield 98.6wt%.
131 are added in the four round flask equipped with reflux condensate device, thermometer, agitator and gas absorbing device
Gram C16H33O(CHCH3CH2O)10(CH2CH2O)21H and 20 gram of pyridine, is heated to 70 DEG C under stirring, use dropping funel
35 grams of thionyl chlorides are slowly added dropwise, are reacted 10 hours at 90 DEG C after completion of dropping.After reaction terminates, reactant is stood,
Cooling layering, neutrality is neutralized to sodium hydroxide solution by upper strata, with saturated common salt water washing 5-6 time of heat, after drying
Obtain intermediate product C16H33O(CHCH3CH2O)10(CH2CH2O)20CH2CH2Cl, yield is 86.6%.
By C16H33O(CHCH3CH2O)10(CH2CH2O)20CH2CH2135 grams of Cl add with reflux condensate device,
In thermometer, the four-hole boiling flask of agitator, 77 DEG C are heated to, by N (C2H5)(C3H6OH) solution is slow with dropping funel
In dripping to flask, system remains alkalescent, stratification after reacting 10 hours.Heat will be used after the vacuum distillation of upper strata
Saturated common salt water washing 5-6 time, obtain desired intermediate C16H33O(CHCH3CH2O)10(CH2CH2O)20
CH2CH2N(C2H5)(C3H7O), yield is 83.3%.
By C16H33O(CHCH3CH2O)10(CH2CH2O)20CH2CH2N(C2H5)(C3H7O) 100 grams are added to band
In having the four-hole boiling flask of reflux condensate device, thermometer, agitator, 60 DEG C are heated to, are slowly added dropwise H2O2Solution 30
Gram, react 5 hours at 70 DEG C, with petroleum ether extraction, vacuum drying, Jing high performance liquid chromatography (HPLC) is analyzed,
C in product16H33O(CHCH3CH2O)10(CH2CH2O)20CH2CH2N(C2H5)(C3H7O) O content is 96.32
Wt%.
(2) preparation of foaming agent combination：
At normal temperatures and pressures, 50 grams of long-chain polyether nitrogen-containing compound obtained by synthesis is weighed in previous step in reactor,
Add appropriate local originally water dissolves；Be added thereto to 66 grams of decane sulfonate again, add it is enough it is local from
Water is configured to the solution of 30wt% to 386 grams, is sufficiently stirred for 30min to being completely dissolved, obtains final product foaming agent
Composition CX-2.
【Embodiment 3】
The preparation of composition CX-3, preparation process：
(1) long-chain polyether nitrogen-containing compound (C14H29OC3H6O(CH2CH2O)8CH2CH2N(C3H7O)2O conjunction)
Into with preparation：
107.0 grams of tetradecanols, 3.0 grams of potassium hydroxide are added in the pressure reactor equipped with agitating device, is heated to
When 80～90 DEG C, vacuum system is opened, be dehydrated under a high vacuum 1 hour, then with nitrogen displacement 3～4 times, by body
It is that reaction temperature is adjusted to 150 DEG C and is slowly passed through 60 grams of expoxy propane, control pressure≤0.60MPa is cooled to 90 DEG C, very
Sky removes low-boiling-point substance, and system reaction temperature is adjusted to 150 DEG C and is slowly passed through 203.0 grams of oxirane, control pressure by continuation
≤0.60MPa.After reaction terminates, neutralization, dehydration, obtain C after cooling14H29OCHCH3CH2O(CH2CH2O)9H,
Yield 98.7wt%.
327 are added in the four round flask equipped with reflux condensate device, thermometer, agitator and gas absorbing device
Gram C14H29OCHCH3CH2O(CH2CH2O)9H and 20 gram of pyridine, is heated to 70 DEG C under stirring, slow with dropping funel
35 grams of thionyl chlorides are added dropwise, are reacted 10 hours at 90 DEG C after completion of dropping.Reaction terminate after, by reactant stand, it is cold
But it is layered, upper strata is neutralized to into neutrality with sodium hydroxide solution, with saturated common salt water washing 5-6 time of heat, must after being dried
To intermediate product C14H29OCHCH3CH2O(CH2CH2O)8CH2CH2Cl, yield is 87%.
By C14H29OCHCH3CH2O(CH2CH2O)8CH2CH2165 grams of Cl is added and is carried reflux condensate device, temperature
In degree meter, the four-hole boiling flask of agitator, 77 DEG C are heated to, by N (C3H6OH)2Solution dropping funel slowly drips to burning
In bottle, system remains alkalescent, stratification after reacting 10 hours.The saturation of heat will be used after the vacuum distillation of upper strata
Brine It 5-6 time, obtains desired intermediate C14H29OCHCH3CH2O(CH2CH2O)8CH2CH2N(C3H7
O)2, yield is 83.3%.
By C14H29OCHCH3CH2O(CH2CH2O)8CH2CH2N(C3H7O)2100 grams are added to reflux condensation mode
In device, thermometer, the four-hole boiling flask of agitator, 60 DEG C are heated to, are slowly added dropwise H2O230 grams of solution, at 70 DEG C
Lower reaction 5 hours, with petroleum ether extraction, vacuum drying, Jing high performance liquid chromatography (HPLC) analysis, in product
C14H29OCHCH3CH2O(CH2CH2O)8CH2CH2N(C3H7O)2O content is 96.71wt%.
(2) preparation of foaming agent combination：
At normal temperatures and pressures, 90 grams of long-chain polyether nitrogen-containing compound obtained by synthesis is weighed in previous step in reactor,
Add appropriate local originally water dissolves；6.1 grams of dodecane sulfonate is added thereto to again, adds enough sheets
Ground running water is configured to the solution of 30wt% to 320 grams, is sufficiently stirred for 30min to being completely dissolved, obtains final product bubble
Foam agent composition CX-3.
【Embodiment 4】
The preparation of composition CX-4, preparation process：
(1) long-chain polyether nitrogen-containing compound (C20H33O(C3H6O)5(CH2CH2O)3CH2CH2N(C3H7)(C5H11)O)
Synthesis with prepare：
145.0 grams of myristyl phenol, 2.0 grams of potassium hydroxide are added in the pressure reactor equipped with agitating device, plus
When heat is to 80～90 DEG C, vacuum system is opened, be dehydrated under a high vacuum 1 hour, then with nitrogen displacement 3～4 times,
System reaction temperature is adjusted to into 150 DEG C and is slowly passed through 300 grams of expoxy propane, control pressure≤0.60MPa is cooled to 90 DEG C,
Low-boiling-point substance is removed in vacuum, system reaction temperature is adjusted to 150 DEG C and is slowly passed through 180.0 grams of oxirane, control pressure by continuation
Power≤0.60MPa.After reaction terminates, neutralization, dehydration, obtain C after cooling20H33O(C3H6O)5(CH2CH2O)4H, receives
Rate 99.6wt%.
218 are added in the four round flask equipped with reflux condensate device, thermometer, agitator and gas absorbing device
Gram C20H33O(C3H6O)5(CH2CH2O)4H and 20 gram of pyridine, is heated to 70 DEG C under stirring, be slowly added dropwise with dropping funel
35 grams of thionyl chlorides, react 10 hours after completion of dropping at 90 DEG C.After reaction terminates, reactant is stood, cooling divides
Layer, neutrality is neutralized to sodium hydroxide solution by upper strata, with saturated common salt water washing 5-6 time of heat, in obtaining after drying
Between product C20H33O(C3H6O)5(CH2CH2O)3CH2CH2Cl, yield is 87.1%.
By C20H33O(C3H6O)5(CH2CH2O)3CH2CH296 grams of Cl add with reflux condensate device, thermometer,
In the four-hole boiling flask of agitator, 77 DEG C are heated to, by N (C3H7)(C5H11) solution dropping funel slowly drips to flask
In, system remains alkalescent, stratification after reacting 10 hours.By the saturation food after the vacuum distillation of upper strata with heat
Salt water washing 5-6 time, obtains desired intermediate C20H33O(C3H6O)5(CH2CH2O)3CH2CH2N(C3H7)(C5H1 1), yield is 83.7%.
By C20H33O(C3H6O)5(CH2CH2O)3CH2CH2N(C3H7)(C5H11) 100 grams be added to reflux condensation mode
In device, thermometer, the four-hole boiling flask of agitator, 60 DEG C are heated to, are slowly added dropwise H2O230 grams of solution, at 70 DEG C
Lower reaction 5 hours, with petroleum ether extraction, vacuum drying, Jing high performance liquid chromatography (HPLC) analysis, in product
C20H33O(C3H6O)5(CH2CH2O)3CH2CH2N(C3H7)(C5H11) O content be 97.61wt%.
(2) preparation of foaming agent combination：
At normal temperatures and pressures, 90 grams of long-chain polyether nitrogen-containing compound obtained by synthesis is weighed in previous step in reactor,
Add appropriate local originally water dissolves；31.2 grams of octadecyl sulfonic acid salt is added thereto to again, is added enough
Local running water is configured to the solution of 30wt% to 404 grams, is sufficiently stirred for 30min to being completely dissolved, obtains final product
Foaming agent combination CX-4.
【Embodiment 5】
The preparation of composition CX-5, preparation process：
(1) long-chain polyether nitrogen-containing compound (C12H25O(CHCH3CH2O)20(CH2CH2O)15CH2CH2N(CH3)(C2H5)
O synthesis) and preparation：
93.0 grams of dodecanols, 5.6 grams of potassium hydroxide are added in the pressure reactor equipped with agitating device, it is heated to 80～
When 90 DEG C, vacuum system is opened, be dehydrated under a high vacuum 1 hour, it is then with nitrogen displacement 3～4 times, system is anti-
Answer temperature to be adjusted to 150 DEG C and be slowly passed through 600 grams of expoxy propane, control pressure≤0.60MPa is cooled to 90 DEG C, vacuum
Low-boiling-point substance is removed, system reaction temperature is adjusted to 150 DEG C and is slowly passed through 720 grams of oxirane, control pressure by continuation
≤0.60MPa.After reaction terminates, neutralization, dehydration, obtain C after cooling12H25O(CHCH3CH2O)20(CH2CH2O)16H,
Yield 98.6wt%.
287 are added in the four round flask equipped with reflux condensate device, thermometer, agitator and gas absorbing device
Gram C12H25O(CHCH3CH2O)20(CH2CH2O)16H and 30 gram of pyridine, is heated to 70 DEG C under stirring, use dropping funel
35 grams of thionyl chlorides are slowly added dropwise, are reacted 10 hours at 90 DEG C after completion of dropping.After reaction terminates, reactant is stood,
Cooling layering, neutrality is neutralized to sodium hydroxide solution by upper strata, with saturated common salt water washing 5-6 time of heat, after drying
Obtain intermediate product C12H25O(CHCH3CH2O)20(CH2CH2O)15CH2CH2Cl, yield is 88%.
By C12H25O(CHCH3CH2O)20(CH2CH2O)15CH2CH2146 grams of Cl add with reflux condensate device,
In thermometer, the four-hole boiling flask of agitator, 77 DEG C are heated to, by N (CH3)(C2H5) solution dropping funel slowly drips
To in flask, system remains alkalescent, stratification after reacting 10 hours.Heat will be used after the vacuum distillation of upper strata
Saturated common salt water washing 5-6 time, obtains desired intermediate C12H25O(CHCH3CH2O)20(CH2CH2O)15CH2CH2
N(CH3)(C2H5), yield is 83.3%.
By C12H25O(CHCH3CH2O)20(CH2CH2O)15CH2CH2N(CH3)(C2H5) 100 grams be added to and carry back
In stream condensing unit, thermometer, the four-hole boiling flask of agitator, 60 DEG C are heated to, are slowly added dropwise H2O230 grams of solution,
React 5 hours at 70 DEG C, with petroleum ether extraction, vacuum drying, Jing high performance liquid chromatography (HPLC) analysis, produce
C in thing12H25O(CHCH3CH2O)20(CH2CH2O)15CH2CH2N(CH3)(C2H5) O content be 96.97wt%.
(2) preparation of foaming agent combination：
At normal temperatures and pressures, 90 grams of long-chain polyether nitrogen-containing compound obtained by synthesis is weighed in previous step in reactor,
Add appropriate local originally water dissolves；7 grams of cetyl sulfonate is added thereto to again, is added enough local
Running water is configured to the solution of 30wt% to 323 grams, is sufficiently stirred for 30min to being completely dissolved, obtains final product foam
Agent composition CX-5.
【Embodiment 6】
The preparation of composition CX-6, preparation process：
(1) long-chain polyether nitrogen-containing compound (C12H25O(CHCH3CH2O)15(CH2CH2O)10CH2CH2
N(CH3)2O synthesis) and preparation：
93.0 grams of dodecanols, 5.6 grams of potassium hydroxide are added in the pressure reactor equipped with agitating device, it is heated to 80～
When 90 DEG C, vacuum system is opened, be dehydrated under a high vacuum 1 hour, it is then with nitrogen displacement 3～4 times, system is anti-
Answer temperature to be adjusted to 150 DEG C and be slowly passed through 450 grams of expoxy propane, control pressure≤0.60MPa is cooled to 90 DEG C, vacuum
Low-boiling-point substance is removed, system reaction temperature is adjusted to 150 DEG C and is slowly passed through 495 grams of oxirane, control pressure by continuation
≤0.60MPa.After reaction terminates, neutralization, dehydration, obtain C after cooling12H25O(CHCH3CH2O)15(CH2CH2O)11H,
Yield 98.6wt%.
269 are added in the four round flask equipped with reflux condensate device, thermometer, agitator and gas absorbing device
Gram C12H25O(CHCH3CH2O)15(CH2CH2O)11H and 57 gram of pyridine, is heated to 70 DEG C under stirring, use dropping funel
85 grams of thionyl chlorides are slowly added dropwise, are reacted 10 hours at 90 DEG C after completion of dropping.After reaction terminates, reactant is stood,
Cooling layering, neutrality is neutralized to sodium hydroxide solution by upper strata, with saturated common salt water washing 5-6 time of heat, after drying
Obtain intermediate product C12H25O(CHCH3CH2O)15(CH2CH2O)10CH2CH2Cl, yield is 88.3%.
By C12H25O(CHCH3CH2O)15(CH2CH2O)10CH2CH2115 grams of Cl add with reflux condensate device,
In thermometer, the four-hole boiling flask of agitator, 77 DEG C are heated to, by N (CH3)2Solution dropping funel slowly drips to flask
In, system remains alkalescent, stratification after reacting 10 hours.By the saturation food after the vacuum distillation of upper strata with heat
Salt water washing 5-6 time, obtains desired intermediate C12H25O(CHCH3CH2O)15(CH2CH2O)10CH2CH2N(CH3)2, yield is 83.8%.
By C12H25O(CHCH3CH2O)15(CH2CH2O)10CH2CH2N(CH3)2100 grams are added to returned cold
In solidifying device, thermometer, the four-hole boiling flask of agitator, 60 DEG C are heated to, are slowly added dropwise H2O230 grams of solution,
React 5 hours at 70 DEG C, with petroleum ether extraction, vacuum drying, Jing high performance liquid chromatography (HPLC) analysis, product
Middle C12H25O(CHCH3CH2O)15(CH2CH2O)10CH2CH2N(CH3)2O content is 97.32wt%.
(2) preparation of foaming agent combination：
At normal temperatures and pressures, 40 grams of long-chain polyether nitrogen-containing compound obtained by synthesis is weighed in previous step in reactor,
Add appropriate local originally water dissolves；45 grams of octadecyl sulfonic acid salt is added thereto to again, adds enough sheets
Ground running water is configured to the solution of 30wt% to 283 grams, is sufficiently stirred for 30min to being completely dissolved, obtains final product bubble
Foam agent composition CX-6.
【Embodiment 7】
The preparation of composition CX-7, preparation process：
(1) long-chain polyether nitrogen-containing compound (C12H25O(CHCH3CH2O)8CH2CH2OCH2CH2N(CH3)2O)
Synthesis with prepare：
93.0 grams of dodecanols, 5.6 grams of potassium hydroxide are added in the pressure reactor equipped with agitating device, it is heated to 80～
When 90 DEG C, vacuum system is opened, be dehydrated under a high vacuum 1 hour, it is then with nitrogen displacement 3～4 times, system is anti-
Answer temperature to be adjusted to 150 DEG C and be slowly passed through 240 grams of expoxy propane, control pressure≤0.60MPa is cooled to 90 DEG C, vacuum
Low-boiling-point substance is removed, system reaction temperature is adjusted to 150 DEG C and is slowly passed through 90 grams of oxirane, control pressure by continuation
≤0.60MPa.After reaction terminates, neutralization, dehydration, obtain C after cooling12H25O(CHCH3CH2O)8(CH2CH2O)2H,
Yield 98.6wt%.
269 are added in the four round flask equipped with reflux condensate device, thermometer, agitator and gas absorbing device
Gram C12H25O(CHCH3CH2O)8(CH2CH2O)2H and 57 gram of pyridine, is heated to 70 DEG C under stirring, slow with dropping funel
Slowly 85 grams of thionyl chlorides are added dropwise, are reacted 10 hours at 90 DEG C after completion of dropping.After reaction terminates, reactant is stood,
Cooling layering, neutrality is neutralized to sodium hydroxide solution by upper strata, with saturated common salt water washing 5-6 time of heat, after drying
Obtain intermediate product C12H25O(CHCH3CH2O)8CH2CH2O CH2CH2Cl, yield is 88.3%.
By C12H25O(CHCH3CH2O)8CH2CH2OCH2CH2115 grams of Cl is added and is carried reflux condensate device, temperature
In meter, the four-hole boiling flask of agitator, 77 DEG C are heated to, by N (CH3)2Solution dropping funel is slowly dripped in flask,
System remains alkalescent, stratification after reacting 10 hours.The saturated aqueous common salt of heat will be used after the vacuum distillation of upper strata
Washing 5-6 time, obtains desired intermediate C12H25O(CHCH3CH2O)8CH2CH2OCH2CH2N(CH3)2, receive
Rate is 83.8%.
By C12H25O(CHCH3CH2O)8CH2CH2OCH2CH2N(CH3)2100 grams are added to reflux condensation mode dress
Put, in the four-hole boiling flask of thermometer, agitator, be heated to 60 DEG C, be slowly added dropwise H2O230 grams of solution, at 70 DEG C
Lower reaction 5 hours, with petroleum ether extraction, vacuum drying, Jing high performance liquid chromatography (HPLC) analysis, in product
C12H25O(CHCH3CH2O)8CH2CH2OCH2CH2N(CH3)2O content is 97.32wt%.
(2) preparation of foaming agent combination：
At normal temperatures and pressures, 40 grams of long-chain polyether nitrogen-containing compound obtained by synthesis is weighed in previous step in reactor,
Add appropriate local originally water dissolves；69.6 grams of dodecane sulfonate is added thereto to again, is added enough
Local running water is configured to the solution of 30wt% to 365 grams, is sufficiently stirred for 30min to being completely dissolved, obtains final product
Foaming agent combination CX-7.
【Embodiment 8】
The preparation of composition CX-8, preparation process：
(1) long-chain polyether nitrogen-containing compound (C14H21O(CHCH3CH2O)6(CH2CH2O)12CH2CH2N(CH3)2O)
Synthesis with prepare：
103.0 grams of octyl phenols, 5.6 grams of potassium hydroxide are added in the pressure reactor equipped with agitating device, is heated to
When 80～90 DEG C, vacuum system is opened, be dehydrated under a high vacuum 1 hour, then with nitrogen displacement 3～4 times, by body
It is that reaction temperature is adjusted to 150 DEG C and is slowly passed through 174 grams of expoxy propane, control pressure≤0.60MPa is cooled to 90 DEG C,
Low-boiling-point substance is removed in vacuum, system reaction temperature is adjusted to 150 DEG C and is slowly passed through 286 grams of oxirane, control pressure by continuation
≤0.60MPa.After reaction terminates, neutralization, dehydration, obtain C after cooling14H21O(CHCH3CH2O)6(CH2CH2O)13H,
Yield 98.6wt%.
269 are added in the four round flask equipped with reflux condensate device, thermometer, agitator and gas absorbing device
Gram C14H21O(CHCH3CH2O)6(CH2CH2O)13H and 57 gram of pyridine, is heated to 70 DEG C under stirring, use dropping funel
85 grams of thionyl chlorides are slowly added dropwise, are reacted 10 hours at 90 DEG C after completion of dropping.After reaction terminates, reactant is stood,
Cooling layering, neutrality is neutralized to sodium hydroxide solution by upper strata, with saturated common salt water washing 5-6 time of heat, after drying
Obtain intermediate product C14H21O(CHCH3CH2O)6(CH2CH2O)12CH2CH2Cl, yield is 88.3%.
By C14H21O(CHCH3CH2O)6(CH2CH2O)12CH2CH2115 grams of Cl add with reflux condensate device,
In thermometer, the four-hole boiling flask of agitator, 77 DEG C are heated to, by N (CH3)2Solution dropping funel slowly drips to flask
In, system remains alkalescent, stratification after reacting 10 hours.By the saturation food after the vacuum distillation of upper strata with heat
Salt water washing 5-6 time, obtains desired intermediate C14H21O(CHCH3CH2O)6(CH2CH2O)12CH2CH2N(CH3)2, yield is 83.8%.
By C14H21O(CHCH3CH2O)6(CH2CH2O)12CH2CH2N(CH3)2100 grams are added to reflux condensation mode
In device, thermometer, the four-hole boiling flask of agitator, 60 DEG C are heated to, are slowly added dropwise H2O230 grams of solution, at 70 DEG C
Lower reaction 5 hours, with petroleum ether extraction, vacuum drying, Jing high performance liquid chromatography (HPLC) analysis, in product
C14H21O(CHCH3CH2O)6(CH2CH2O)12CH2CH2N(CH3)2O content is 97.32wt%.
(2) preparation of foaming agent combination：
At normal temperatures and pressures, 40 grams of long-chain polyether nitrogen-containing compound obtained by synthesis is weighed in previous step in reactor,
Add appropriate local originally water dissolves；82.1 grams of tetradecyl sulfonate is added thereto to again, is added enough
Local running water is configured to the solution of 30wt% to 407 grams, is sufficiently stirred for 30min to being completely dissolved, obtains final product
Foaming agent combination CX-8.
【Embodiment 9】
The preparation of composition CX-9, preparation process：
(1) long-chain polyether nitrogen-containing compound (C10H21O(CHCH3CH2O)3(CH2CH2O)7CH2CH2N(CH3)2O)
Synthesis with prepare：
172.0 grams of decane alcohol, 5.6 grams of potassium hydroxide are added in the pressure reactor equipped with agitating device, it is heated to 80～
When 90 DEG C, vacuum system is opened, be dehydrated under a high vacuum 1 hour, it is then with nitrogen displacement 3～4 times, system is anti-
Answer temperature to be adjusted to 150 DEG C and be slowly passed through 179.9 grams of expoxy propane, control pressure≤0.60MPa is cooled to 90 DEG C, very
Sky removes low-boiling-point substance, and system reaction temperature is adjusted to 150 DEG C and is slowly passed through 360.0 grams of oxirane, control pressure by continuation
≤0.60MPa.After reaction terminates, neutralization, dehydration, obtain C after cooling10H21O(CHCH3CH2O)3(CH2CH2O)8H,
Yield 98.7wt%.
325 are added in the four round flask equipped with reflux condensate device, thermometer, agitator and gas absorbing device
Gram C10H21O(CHCH3CH2O)3(CH2CH2O)8H and 57 gram of pyridine, is heated to 70 DEG C under stirring, slow with dropping funel
Slowly 85 grams of thionyl chlorides are added dropwise, are reacted 10 hours at 90 DEG C after completion of dropping.After reaction terminates, reactant is stood,
Cooling layering, neutrality is neutralized to sodium hydroxide solution by upper strata, with saturated common salt water washing 5-6 time of heat, after drying
Obtain intermediate product C10H21O(CHCH3CH2O)3(CH2CH2O)7CH2CH2Cl, yield is 88.1%.
By C10H21O(CHCH3CH2O)3(CH2CH2O)7CH2CH2137 grams of Cl is added and is carried reflux condensate device, temperature
In degree meter, the four-hole boiling flask of agitator, 77 DEG C are heated to, by N (CH3)2Solution dropping funel is slowly dripped in flask,
System remains alkalescent, stratification after reacting 10 hours.The saturated aqueous common salt of heat will be used after the vacuum distillation of upper strata
Washing 5-6 time, obtains desired intermediate C10H21O(CHCH3CH2O)3(CH2CH2O)7CH2CH2N(CH3)2,
Yield is 83.7%.
By C10H21O(CHCH3CH2O)3(CH2CH2O)7CH2CH2N(CH3)2100 grams are added to reflux condensation mode
In device, thermometer, the four-hole boiling flask of agitator, 60 DEG C are heated to, are slowly added dropwise H2O230 grams of solution, at 70 DEG C
Lower reaction 5 hours, with petroleum ether extraction, vacuum drying, Jing high performance liquid chromatography (HPLC) analysis, in product
C10H21O(CHCH3CH2O)3(CH2CH2O)7CH2CH2N(CH3)2O content is 97.33wt%.
(2) preparation of foaming agent combination：
At normal temperatures and pressures, 40 grams of long-chain polyether nitrogen-containing compound obtained by synthesis is weighed in previous step in reactor,
Add appropriate local originally water dissolves；33 grams of tetradecyl sulfonate is added thereto to again, adds enough sheets
Ground running water is configured to the solution of 30wt% to 243 grams, is sufficiently stirred for 30min to being completely dissolved, obtains final product bubble
Foam agent composition CX-9.
The foam discharging agent component structure of table 1
| Foam discharging agent | R1 | y | z | R2 | R3 | R4 | R5 | I and II mol ratio |
| CX-1 | C12H25 | 3 | 7 | C2H4 | CH3 | CH3 | C12H25 | 1:2 |
| CX-2 | C16H33 | 10 | 20 | C2H4 | C2H5 | C3H7O | C10H21 | 1:10 |
| CX-3 | C14H29 | 1 | 8 | C2H4 | C3H7O | C3H7O | C12H25 | 1:0.2 |
| CX-4 | C20H33 | 5 | 3 | C2H4 | C3H7 | C5H11 | C18H37 | 1:1 |
| CX-5 | C12H25 | 20 | 15 | C2H4 | C2H5 | CH3 | C16H33 | 1:0.5 |
| CX-6 | C12H25 | 15 | 10 | C2H4 | CH3 | CH3 | C18H37 | 1:5 |
| CX-7 | C12H25 | 8 | 1 | C2H4 | CH3 | CH3 | C12H25 | 1:5 |
| CX-8 | C14H21 | 6 | 12 | C2H4 | CH3 | CH3 | C14H29 | 1:8 |
| CX-9 | C10H21 | 3 | 7 | C2H4 | CH3 | CH3 | C14H29 | 1:2 |
【Embodiment 10】
Prepare salinity and be respectively 80000mg/L, the simulation water of 150000mg/L, 200000mg/L, with reference to SY/T
6450-2000《Foam drainage gas recovery foaming agent evaluation method》Standard, determines foaming power, the foam stabilization of foam discharging agent
The performances such as property, fluid-carrying capability.The results are shown in Table shown in 2.
The foaming properties of the foam discharging agent composition in the embodiment of table 2
【Comparative example 1】
Use【Embodiment 1】The C of middle synthesis12H25O(CHCH3CH2O)3(CH2CH2O)7CH2CH2N(CH3)2O,
【Embodiment 2】The C of middle synthesis16H33O(CHCH3CH2O)10(CH2CH2O)20CH2CH2N(C2H5)(C3H7O) O,
【Embodiment 3】The C of middle synthesis14H29OC3H6O(CH2CH2O)8CH2CH2N(C3H7O)2O,【Embodiment 4】In
The C of synthesis20H33O(C3H6O)5(CH2CH2O)3CH2CH2N(C3H7)(C5H11) O single dose, be added without subsequent component
Foaming agent combination is prepared into, together【Embodiment 10】Foaming properties test is carried out, be the results are shown in Table shown in 3.
【Comparative example 2】
Respectively using dodecyl sodium sulfate, myristyl sodium sulfonate, sodium cetanesulfonate single dose, together【Embodiment
10】Foaming properties test is carried out, be the results are shown in Table shown in 3.
【Comparative example 3】
At normal temperatures and pressures, weigh 70 grams of DDAO in reactor, add it is appropriate it is local from
Carry out water dissolves；103 grams of dodecyl sodium sulfates are added thereto to again, add enough local running water to 576 grams,
The solution of 30wt% is configured to, 30min is sufficiently stirred for being completely dissolved, foaming agent combination CX-10 is obtained final product,
Together【Embodiment 10】Foaming properties test is carried out, as a result to be shown in Table 3.
The foaming properties of the foam discharging agent single dose in the comparative example of table 3
Claims (9)
1. a kind of resistance to salinity water pumping gas production foam discharging agent composition, in terms of molfraction, including following components：
(1) 1 part of long-chain polyether nitrogen-containing compound；
(2) 0.5～20 parts of alkylsulfonate；
Described long-chain polyether nitrogen-containing compound has following general molecular formula：
In formula (I), R1For C8～C30Fat-based；Y adds sum, y=0～20 for PO segments；Z is EO segments
Plus sum, z=0～60；R2For C1～C4Alkylidene；R3、R4For C1～C5Alkyl, replace alkyl in
Any one.
2. resistance to salinity water pumping gas production foam discharging agent composition according to claim 1, it is characterised in that
The R1For C10～C20Alkyl, alkylbenzene at least one.
3. resistance to salinity water pumping gas production foam discharging agent composition according to claim 1, it is characterised in that
The R2For C2H4Or C3H6。
4. resistance to salinity water pumping gas production foam discharging agent composition according to claim 1, it is characterised in that
Y=1～20；Z=1～30.
5. resistance to salinity water pumping gas production foam discharging agent composition according to claim 1, it is characterised in that
Described alkylsulfonate has following general molecular formula：
[R5SO3] jM, formula (II)；
R in formula (II)5For C5～C30Alkyl, M for make molecule shown in formula (II) in it is electroneutral sun from
Son, j is the number of M, and the value of j is the inverse of M valence state values.
6. resistance to salinity water pumping gas production foam discharging agent composition according to claim 1, it is characterised in that
The long-chain polyether nitrogen-containing compound is 1 with the mol ratio of alkylsulfonate:(0.2～10).
7. claim 1～6 arbitrary described resistance to salinity water pumping gas production preparation method of foam discharging agent composition,
Comprise the following steps：
(1) synthesis of long-chain polyether nitrogen-containing compound
A, in the presence of base catalyst, R1OH obtains R with aequum propylene oxide reaction1O
(CHCH3CH2O)yH；
B, in the presence of base catalyst, R1O(CHCH3CH2O)yH is obtained with aequum reacting ethylene oxide
R1O(CHCH3CH2O)y(CH2CH2O)z+1H；
C, by R1O(CHCH3CH2O)y(CH2CH2O)z+1H reacts Jing after processing with thionyl chloride and obtains
R1O(CHCH3CH2O)y(CH2CH2O)zR2Cl；
D, by R1O(CHCH3CH2O)y(CH2CH2O)z R2Cl and NR3R4In a solvent, in reaction temperature
70～90 DEG C of reactions obtain R Jing after processing1O(CHCH3CH2O)y(CH2CH2O)z R2NR3R4；
E, by R1O(CHCH3CH2O)y(CH2CH2O)z R2NR3R4React at 60～70 DEG C with hydrogen peroxide,
Long-chain polyether nitrogen-containing compound is obtained Jing after processing；
(2) preparation of foam discharging agent composition
The desired amount of long-chain polyether nitrogen-containing compound, alkylsulfonate are well mixed into obtain resistance to salinity water pumping gas production
Use foam discharging agent composition.
8. claim 1～6 arbitrary described resistance to salinity water pumping gas production application of foam discharging agent composition.
9. the resistance to salinity water pumping gas production according to claim 8 application of foam discharging agent composition, it is special
Levy be suitable for gas well formation water salinity be 0～250000mg/L.
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