CN109679615A - The method that ultra-deep gas well uses the water pumping gas production of foaming water discharge agent composition - Google Patents
The method that ultra-deep gas well uses the water pumping gas production of foaming water discharge agent composition Download PDFInfo
- Publication number
- CN109679615A CN109679615A CN201710969702.4A CN201710969702A CN109679615A CN 109679615 A CN109679615 A CN 109679615A CN 201710969702 A CN201710969702 A CN 201710969702A CN 109679615 A CN109679615 A CN 109679615A
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- CN
- China
- Prior art keywords
- water discharge
- agent composition
- discharge agent
- foaming
- foaming water
- Prior art date
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 133
- 238000005187 foaming Methods 0.000 title claims abstract description 83
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 81
- 239000000203 mixture Substances 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000005086 pumping Methods 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 229920000768 polyamine Polymers 0.000 claims abstract description 57
- 229920000570 polyether Polymers 0.000 claims abstract description 52
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 44
- 239000000243 solution Substances 0.000 claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 150000003839 salts Chemical class 0.000 claims abstract description 12
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- 239000007789 gas Substances 0.000 claims description 66
- -1 hydrocarbon radical Chemical class 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 35
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- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
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- 238000011938 amidation process Methods 0.000 claims description 2
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- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- 229940126062 Compound A Drugs 0.000 claims 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 229910019142 PO4 Inorganic materials 0.000 claims 1
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- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 1
- 239000003245 coal Substances 0.000 claims 1
- 150000002240 furans Chemical class 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 238000007210 heterogeneous catalysis Methods 0.000 claims 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims 1
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- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 description 1
- 229940073769 methyl oleate Drugs 0.000 description 1
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000002467 phosphate group Chemical class [H]OP(=O)(O[H])O[*] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- KPFSGNRRZMYZPH-UHFFFAOYSA-M potassium;2-chloroacetate Chemical class [K+].[O-]C(=O)CCl KPFSGNRRZMYZPH-UHFFFAOYSA-M 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 150000008053 sultones Chemical class 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000004711 α-olefin 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
-
- 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
-
- 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)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Geology (AREA)
- Mining & Mineral Resources (AREA)
- Physics & Mathematics (AREA)
- Environmental & Geological Engineering (AREA)
- Fluid Mechanics (AREA)
- Geochemistry & Mineralogy (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of methods that ultra-deep gas well uses the water pumping gas production of foaming water discharge agent composition, mainly solve existing foaming water discharge agent containing H2S、CO2Resisting high temperature, high salt performance is poor under acidic environment, and high temperature and high salt ultra-deep gas well can not be solved the problems, such as because of the underproduction even stop-spraying caused by hydrops.The present invention is by using the following steps are included: foaming water discharge agent composition and water are mixed to get foaming water discharge agent composition solution by (1);(2) mixed solution of foaming water discharge agent composition solution or foaming water discharge agent composition solution and oil is come into full contact with gas, formation aerated fluid, by the foaming water discharge agent composition solution water or oil water mixture displacement come out;The foaming water discharge agent composition is in terms of mass fraction including following components: 1) 1 part of polyamines polyether compound;2) technical solution of 0.01~100 portion of cosurfactant preferably resolves the problem, can be used in acidic high-temperature ultra-deep gas well water pumping gas production with high salt.
Description
Technical field
The present invention relates to a kind of methods that ultra-deep gas well uses the water pumping gas production of foaming water discharge agent composition.
Background technique
With the reinforcement of gas-field exploitation dynamics, gas field is discharged the critical issue normally produced at gas well is restricted.Foam row
Hydromining gas is a kind of drainage gas recovery that recent domestic rapidly develops, simple, easy for construction, at low cost with equipment,
Applicable well depth range is big, does not influence the advantages that gas well normally produces.Foaming water discharge is exactly to pass through oil pipe or tubing and casing annular space to well
Interior injection foaming water discharge agent generates the foam with certain stability under the agitation of air-flow.The liquid phase that deposition is slipped in pipe becomes
For foam, change the relative density of lower curtate bit stream body in managing, quantity-produced gas phase displacement foam flows out pit shaft, so that well be discharged
Interior hydrops, achievees the purpose that water pumping gas production.
The development of foreign countries' foaming water discharge agent since the eighties of last century sixties, multiselect sulfonate, benzene sulfonate, alkyl
The surfactants such as phenol polyethenoxy ether.Recompounded multielement system is mostly used greatly with foaming water discharge agent to current water pumping gas production, in order to
Enhance the stability of single foam, the auxiliary agents such as alkali, alcohol, polymer, alkanolamide are usually additionally added in formula and form strengthening foam.
US7122509 reports a kind of high temperature foam draining agent prescription, the Research Thinking neutralized using anionic surfactant plus amine,
The heat resistance of raising system is not directed to drainage effect in patent and uses concentration.US20120279715 reports a kind of gas
Gas recovery increases the aerated fluid of oil yield in well, is that a kind of phosphinylidyne-containing amine group quaternary surfactant has both foaming water discharge
And sterilizing function, hydrophobic chain are the hydrophobic patch replaced in naphthalene nucleus, phenyl ring or natural grease, have very strong chlorine-resistant and anticoagulant analysis
The performance of oil also has good corrosion inhibition, the foaming agent of activity concentration 400ppm, foaming water discharge rate in tap water
86.8%, salinity is the analog salt bubbly water foam discharge rate 79.1% of 130000mg/L, however due to containing in molecular structure
The amide group more sensitive to high temperature, thus it is poor to 100 DEG C or more of gas well adaptability.China is from the eighties in last century
Year begins one's study foam drainaging gas cutting process technology, and patent CN102212348A discloses a kind of salt tolerant, methanol tolerance foaming water discharge
Agent, each component content by weight percentage are as follows: Cocoamidopropyl betaine 20~40%, amine oxide 45~65%, alpha-olefin
Sulfonate 5~20%, triethanolamine 5~15%, fluorocarbon surfactant 0.2~2%, methanol 0~5%, can be resistant to salinity
Up to 180,000, foaming agent dosage 5000ppm, but the agent contains fluorocarbon surfactant, and not only cost greatly improves and to environment
It is affected.
The above results show that resisting high temperature, high salt performance difference is the main of restriction high temperature ultra-deep gas well foaming water discharge technology development
Factor.
Summary of the invention
High temperature resistance that the technical problem to be solved by the present invention is to existing foaming water discharge agents under acidic environment is poor, can not
High temperature ultra-deep gas well is solved the problems, such as because of the underproduction even stop-spraying caused by hydrops, provides a kind of ultra-deep gas well using foaming water discharge
The method of agent composition water pumping gas production is applied to high temperature deep well, has very good heat resistance in acid condition, has
Liquid, blistering and foam stability energy are taken by force.
One of to solve above-mentioned technical problem, The technical solution adopted by the invention is as follows: a kind of ultra-deep gas well uses foam
The method of water discharge agent composition water pumping gas production, comprising the following steps:
(1) foaming water discharge agent composition and water are mixed to get foaming water discharge agent composition solution;
(2) foaming water discharge agent composition solution or foaming water discharge agent composition solution and the mixed solution of oil are filled with gas
Tap touching, formed aerated fluid, by the foaming water discharge agent composition solution water or oil water mixture displacement come out;
Wherein, the foaming water discharge agent composition, in terms of mass fraction, including following components:
1) 1 part of polyamines polyether compound;
2) 0.01~100 portion of cosurfactant;
Wherein, the polyamines polyether compound is with general molecular formula shown in formula (1):
In formula (1), R1Selected from C4~C32One of alkyl or substituted hydrocarbon radical, R2、R3、R4It is independently selected from H, C1~C5Alkyl
Carboxylate or substituted hydrocarbon radical carboxylate, C1~C5Hydrocarbyl sulfonate or substituted hydrocarbyl sulfonic acid salt, C1~C5Hydrocarbyl phosphate salt or substitution
Hydrocarbyl phosphate salt and C1~C5At least one of sulfovinic acid ester salt or substituted hydrocarbon radical sulfuric acid, and be not simultaneously H;M is-N
(A)CH2CH2The number of segment, m=1~10;A is substituent group shown in formula (4);S1, s2, s3 are the adduction that propoxyl group rolls into a ball PO
Number, s1=0~30, s2=0~30, s3=0~30;R1, r2, r3 are the adduction number of ethoxy group EO, r1=0~30, r2=0
~30, r3=0~30, and s1+s2+m*s3 and r1+r2+m*r3 are not zero simultaneously;
The gas is at least one of air, nitrogen, methane or natural gas, can contain or not contain H2S or CO2
Sour gas;The oil is at least one of kerosene, crude oil or condensate.
In above-mentioned technical proposal, the cosurfactant is preferably selected from amphoteric ion or cationic surfactant, yin
At least one of ionic surface active agent;The amphoteric ion or cationic surfactant preferably have to be divided shown in formula (2)
Sub- general formula:
In formula (2), R5For selected from C4~C32One of alkyl or substituted hydrocarbon radical, R6、R7It is independently selected from (CH2)aOH or
(CH2)bCH3One of, R8Selected from (CH2)aOH、(CH2)bCH3、(CH2)cOr (CH2)c(CHOH)d(CH2)eOne of, a=
Any integer in 2~4, any integer in b=0~5, any integer in c=1~4, any integer in d=0~3,
Any integer in e=1~4;N is the adduction number that propoxyl group rolls into a ball PO, n=0~15;P is the adduction number of ethoxy group EO, p=0
~30;X-For selected from OH-, halogen anion, HCO3 -、NO3 -、CH3OSO3 -、CH3COO-、COO-、SO3 -Or OSO3 -One of;
The anionic surfactant preferably has general molecular formula shown in formula (3):
In formula (3), R9With R10The sum of for selected from C4~C32One of alkyl or substituted hydrocarbon radical, M be selected from hydrogen, alkali metal or
Person is by formula NR11(R12)(R13)(R14) shown at least one of group, R11、R12、R13、R14To be independently selected from H, (CH2)aOH or
(CH2)bCH3One of, any integer in a=2~4, b=0~5.
In above-mentioned technical proposal, R1、R5Preferably C8~C24Alkyl or substituted hydrocarbon radical.
In above-mentioned technical proposal, R2、R3、R4Independent is preferably H, CH2COOM1、(CH2)3SO3M1Or CH2(CHOH)
CH2SO3M1One of, and be not simultaneously H.
In above-mentioned technical proposal, R6、R7Preferably CH3、C2H5、(CH2)2OH or C6H5CH2One of.
In above-mentioned technical proposal, the R8Preferably CH3、C2H5、(CH2)2OH or C6H5CH2One of;Or R8X-It is preferred that
For CH2COO-、(CH2)3SO3 -、CH2(CHOH)CH2SO3 -One of.
In above-mentioned technical proposal, R9With R10The sum of preferably C7~C23Alkyl or substituted hydrocarbon radical.
In above-mentioned technical proposal, M and M1Independent is preferably hydrogen, alkali metal or by formula NR11(R12)(R13)(R14) shown in base
At least one of group.
In above-mentioned technical proposal, R11、R12、R13、R14Independent is preferably H, (CH2)aOH or (CH2)bCH3One of.
In above-mentioned technical proposal, preferably a=2~4, b=0~5.
In above-mentioned technical proposal, preferred m=1~5.
In above-mentioned technical proposal, preferred n=0~5;P=0~5.
In above-mentioned technical proposal, preferably s1+s2+m*s3=0~5, r1+r2+m*r3=0~10, and s1+s2+m*s3 and
R1+r2+m*r3 is not zero simultaneously;Further preferred s1+s2+m*s3=1~5, r1+r2+m*r3=1~10.
In above-mentioned technical proposal, it is preferred to steep the mass ratio of polyamines polyether compound and cosurfactant in drain combination object
It is 1: (0.1~10).
In above-mentioned technical proposal, gas preferably is selected from least one of nitrogen, methane or natural gas.
H in above-mentioned technical proposal, in gas2S and CO2Content be preferably 15~35%.
In above-mentioned technical proposal, oil preferably is selected from least one of kerosene or condensate.
The foaming water discharge agent composition key active ingredient that the present invention is suitable for ultra-deep gas well is (1) and (2), this field skill
Art personnel know, for the ease of transporting and storing or scene uses etc. considers, can use various supply forms, such as not
Aqueous solid-state form perhaps aqueous solid-state form perhaps aqueous cream form or aqueous solution form;Aqueous solution shape
Formula includes that the form of concentrate is made into water, is directly made into the solution form of concentration needed for scene drains;Wherein, to water without spy
It is different to require, it can be deionized water, can also be the water containing inorganic mineral, and the water containing inorganic mineral can be originally
Water, gas field water flooding.
In above-mentioned technical proposal, the preparation method of the foaming water discharge agent composition, comprising the following steps:
(1) preparation of polyamines polyether compound
A, amidation process:
By R0COOR ' and H (NHCH2CH2)mNH2, catalyst is with molar ratio 1:(1~2): (0~0.5) mixing, under stirring in
50~200 DEG C of reaction temperature are reacted 3~15 hours, and alcohol or water that reaction generates are evaporated off under normal pressure or reduced pressure, can obtain
To required amide compound R0CO(NHCH2CH2)mNH2;Wherein, R0Selected from C3~C31One of alkyl or substituted hydrocarbon radical, R '
Selected from H, it is selected from C1~C8Alkyl, c=1~10, catalyst be selected from alkali metal hydroxide, alkali metal alcoholates, alkali metal carbonic acid
At least one of salt;
B, reduction reaction:
R0CO(NHCH2CH2)mNH2The method that catalytic hydrogenation can be used in the reduction of middle amide occurs non-equal at high temperature under high pressure
Phase catalytic reaction generates corresponding amine, or uses: the R that step a is synthesized0CO(NHCH2CH2)mNH2With metal hydride H-Y+?
Reduction reaction is carried out in aprotic solvents, obtains R0CH2(NHCH2CH2)cNH2.Wherein, Y+For metallic compound, metal alkyl
Compound, metal amide.
C, poly- etherification reaction:
In the presence of basic catalyst, R that step b is synthesized0CH2(NHCH2CH2)mNH2Successively with aequum epoxy third
Alkane, reacting ethylene oxide obtain long-chain polyamines polyethers intermediate product R0CH2{N[(CHCH3CH2O)s3(CH2CH2O)r3H]
[CH2CH2]}mN[(CHCH3CH2O)s1(CH2CH2O)r1H][CHCH3CH2O)s2(CH2CH2O)r2)H];
D, carboxylation or sulfonating reaction:
The long-chain polyamines polyethers intermediate product and ionization reagent and alkali that step c is obtained are with molar ratio 1:(1~5): (1
~10) it in a solvent, reacts to generate for 3~20 hours in 50~120 DEG C of reaction temperature and there is polyamines polyethers shown in structural formula (1)
Carboxylate or polyamines polyether sulfonate;The ionization reagent is selected from XR15Y1Or X R '15Y′1At least one of;Described
Alkali is selected from alkali metal hydroxide or alkali metal alcoholates;Y1With Y '1For SO3M1Or COON1, M1And N1For alkali metal, X is chlorine, bromine
Or iodine;
(2) according to required mass fraction, by the polyamines polyether compound of step (1) synthesis, cosurfactant, mixing is equal
It is even, the foaming water discharge agent composition is made.
In above-mentioned technical proposal, R in step a1COOR’、H(NHCH2CH2)mNH2, catalyst mole preferably than 1:(1~
1.3): (0~0.1).
In above-mentioned technical proposal, in step a catalyst be preferably sodium hydroxide, potassium hydroxide, sodium carbonate, in potassium carbonate
It is at least one.
In above-mentioned technical proposal, H in step b-Y+Preferably LiAlH4、LiAlH(OEt)3Or NaBH4At least one of.
In above-mentioned technical proposal, in step b aprotic solvents be preferably ether, tetrahydrofuran, in dioxane extremely
Few one kind.
In above-mentioned technical proposal, long-chain polyamines polyethers intermediate product in step d: ionization reagent: the molar ratio of alkali is preferred
It is 1: (1~2): (1~4).
In above-mentioned technical proposal, solvent described in step d preferably is selected from C3~C8Ketone and C6~C9Aromatic hydrocarbons at least one
Kind, for example, by acetone, butanone, pentanone, from the substance group that benzene, toluene or dimethylbenzene, trimethylbenzene, ethylbenzene and diethylbenzene form
It is at least one.
In above-mentioned technical proposal, the XR15Y1Or X R '15Y′1Example have but be not limited to chloroacetic alkali metal salt, bromine
The alkali metal salt of acetic acid, the alkali metal salt of 3- chlorine-2-hydroxyl propane sulfonic acid, 2- chloroethanes sulfonic acid alkali metal salts etc..
The foaming water discharge agent composition that the present invention is suitable for ultra-deep gas well has good compatibility, can also contain capable
The common other inorganic agents in domain.
In above-mentioned technical proposal, the ultra-deep gas well for example but not limits preferred high temperature acid gas-containing gas reservoir, stratum temperature
Degree is 150~200 DEG C, the total salinity 5000~200000mg/L, H of formation brine2S and CO2Content 0~35%.
What the present invention used contains the long-chain polyamines compound for stablizing chemical bond, can be to avoid under acidic high-temperature high salt conditions
Hydrolysis, keep the stability of molecular structure, utmostly keep foaming water discharge agent foaming water discharge ability.It is of the present invention
The method of the exactly this water pumping gas production suitable for ultra-deep gas well.
The thermal decomposition temperature of polyamines polyether carboxylation prepared by the present invention or polyamines polyether sulfonate at 200 DEG C or more,
It is not hydrolyzed in acidic aqueous solution or very micro hydrolysis, there is good heat resistance;In molecule non-ionic segment and
On the one hand more hydrophilic groups increase salt-resistance, the amount of the combination water and irreducible water that carry foaming agent increases, foam
Liquid carry over enhancing, analysis liquid slow down;Secondly, increasing foam simultaneous with the functional group of yin, yang opposite-sign in foaming water discharge agent
In the adsorbance of gas-liquid interface, the composition of formation is more efficient for agent;In addition, making in molecule containing the hetero atom responded to pH
Obtaining it can be during the acidic high-temperature that low concentration is applied to 150 DEG C or more ultradeep well water pumping gas production with high salt.
It is related to the occasion of foam discharging agent content or concentration in the present invention, refers both to containing component in above-mentioned technical proposal (1)
(2) total content or total concentration.
The method of liquid discharging gas producing of the present invention can also include the methods of gaslift commonly used in the art, machine pumping.
The present invention, which uses the foaming for measuring foaming water discharge agent, foam stabilizing and takes fluidity, can be carried out bubble row's performance evaluation, pass through height
It foaming, foam stabilizing and takes fluidity before and after warm aging and can be carried out comparison, evaluate the high temperature resistance of foaming water discharge agent, specific evaluation method
Are as follows:
(1) bubble row performance
First using the starting foaming height and certain time of Roche foam meter (ROSS-Miles method) measurement foaming water discharge agent
Foaming height afterwards evaluates its foaming capacity and foam stabilizing ability.The gas of certain flow rate is continuously passed through foaming water discharge agent solution
Or foaming water discharge agent solution and oily mixed solution, foam is formed, (water, can also for the measurement liquid that foamover goes out after a certain period of time
Think You Heshui) amount, it calculates and takes liquid rate, evaluate its fluid-carrying capability.
(2) high temperature resistance
Bubble row's performance and Nai Gao after foaming water discharge agent solution high temperature ageing, will be re-started using the acidproof aging equipment of pressure resistance
Warm performance measurement.
Using the method for liquid discharging gas producing of the invention, 0.02~0.12% foaming water discharge agent is in 0~200,000mg/L mine
In change degree salt water, before and after 180 DEG C of high temperature ageings, foam height reaches 175mm, takes liquid rate up to 93.9%, have in acidic environment
There is excellent heat-resistant salt-resistant, blister and take fluidity energy, achieves preferable technical effect.
Below by embodiment, the present invention is further elaborated.
Detailed description of the invention
Fig. 1 is measurement foaming water discharge agent liquid carry over flow diagram.Wherein, 1 is thermostatical water bath, and 2 be measuring cup, and 3 be to follow
Ring water, 4 be foam collection device, and 5 be foaming tube, and 6 be test solution, and 7 be spinner flowmeter, and 8 be gas cylinder.
Specific embodiment
In order to better understand the present invention, the content that the present invention is further explained with reference to embodiments, but it is of the invention
Content is not limited solely to the following examples.
[embodiment 1]
(1) preparation of foam discharging agent FM01
A, 127.6 grams are added in the reaction flask of Xiang Peiyou mechanical stirring, thermometer, dropping funel and atmospheric distillation plant
(0.55 mole) pentaethylene hexamine and 1.4 grams of (0.025 mole) potassium hydroxide solids, 148 grams are slowly instilled under stirring, and (0.5 rubs
You) methyl oleate, reacts 6 hours in 120~160 DEG C of reaction temperature, is collected simultaneously the methanol that reaction generates, can be obtained required
Amide compound C17H33CO(NHCH2CH2)5NH2, yield 93.8%.
B, reflux condensing tube will be housed, dropping funel is added after water removal in the three-necked flask device of thermometer is clean
11.4 grams of lithium aluminium hydride reduction (0.3 mole) and 90 milliliters of dry dioxane, are dispersed with stirring mixing, are added dropwise at -10~5 DEG C and contain 49.6
Gram (0.1 mole) C17H33CO(NHCH2CH2)5NH240wt% dioxane solution, drip slowly be warming up to 35 DEG C or so it is anti-
It answers 3 hours.Reaction solution is carefully poured into ice water, it is post-treated to obtain long-chain polyamines compound C17H33CH2(NHCH2CH2)5NH2, yield 89.0%.
C, 192.8 grams of (0.4 mole) C are added into the pressure reactor equipped with agitating device17H33CH2(NHCH2CH2)5NH2, 4.0 grams of potassium hydroxide, successively with 469.8 grams of (8.1 moles) propylene oxide, 52.8 grams of (1.2 moles) ethylene oxide 140
~160 DEG C of reactions obtain 1 (R of long-chain polyamines polyether compound1=C18H35, m=5, s1+s2+5s3=20, r1+r2+5r3=3,
R2=R3=R4=H), yield 96.2%.
D, 1 (R of long-chain polyamines polyether compound1=C18H35, m=5, s1+s2+5s3=20, r1+r2+5r3=3, R2=R3
=R4=H) 177.4 grams (0.1 moles) and 8.0 grams of (0.2 mole) sodium hydroxides, 29.5 grams of (0.15 mole) 3- chlorine-2-hydroxyls
Propanesulfonate and 300 milliliters of toluene/benzene (v/v=1) are mixed in four mouthfuls of burnings equipped with mechanical stirring, thermometer and reflux condensing tube
In bottle, it is heated to 90 DEG C and reacts 7 hours.Solvent is evaporated off, obtains 1 (R of long-chain polyamines polyether compound1=C18H35, m=5, s1+s2
+ 5s3=20, r1+r2+5r3=3) hydroxypropionate sodium (R2、R3、R4One of them is CH2CH(OH)CH2SO3Na, remaining is
H)。
E, by 1 (R of long-chain polyamines polyether compound1=C18H35, m=5, s1+s2+5s3=20, r1+r2+5r3=3) hydroxyl
Base propanesulfonate (R2、R3、R4One of them is CH2CH(OH)CH2SO3Na, remaining is H) 50 grams, C16H33OC2H4N+(CH3)3Br-
40 grams, C16H33SO3It 10 grams of K, is uniformly mixed after adding water, the foaming water discharge agent FM01 of 30% content is made.
(2) FM01 is dissolved in deionized water, 100,000mg/L respectively, in 200,000mg/L NaCl water, is configured to
The foam discharging agent mother liquor of 0.3wt%.It is added in Roche foam meter after mother liquor is diluted to a certain concentration, is surveyed using ROSS-Miles method
Determine the starting foaming height and foaming height after five minutes of foam discharging agent FM01, the results are shown in Table 1.
The nitrogen of 4000mL/min is continuously passed through foam discharging agent FM01 aqueous solution, foamover in 15 minutes is measured and goes out
Water, calculating take liquid rate, the results are shown in Table 1.The liquid carry over measurement device of use is as shown in Figure 1.It is acidproof old using pressure resistance
Makeup is set and is tested, and after 180 DEG C of agings for 24 hours, redeterminates starting foaming height, after five minutes foaming height and 15 minutes
The performances such as liquid rate are taken, the results are shown in Table 1.
[embodiment 2]
With [embodiment 1], pH is adjusted to 7 and 4 simulation neutrality and acidity when measuring FM01 performance, with hydrochloric acid by difference
Gaseous environment the results are shown in Table shown in 2.
[embodiment 3]
With [embodiment 1], the difference is that by 1 (R of long-chain polyamines polyether compound1=C18H35, m=5, s1+s2+5s3
=20, r1+r2+5r3=3) hydroxypropionate sodium (R2、R3、R4One of them is CH2CH(OH)CH2SO3Na, remaining is H) 50
Gram, C16H33OC2H4N+(CH3)3Br-It 50 grams, is uniformly mixed after adding water, the foaming water discharge agent FM02 of 30% content is made, as a result sees
Shown in table 3.
[embodiment 4]
With [embodiment 1], the difference is that by 1 (R of long-chain polyamines polyether compound1=C18H35, m=5, s1+s2+5s3
=20, r1+r2+5r3=3) hydroxypropionate sodium (R2、R3、R4One of them is CH2CH(OH)CH2SO3Na, remaining is H) 50
Gram, C16H33SO3It 50 grams of Na, is uniformly mixed after adding water, the foaming water discharge agent FM03 of 35% content is made, the results are shown in Table shown in 4.
[embodiment 5]
(1) preparation of foam discharging agent FM04:
A, 67.0 grams are added in the reaction flask of Xiang Peiyou mechanical stirring, thermometer, dropping funel and atmospheric distillation plant
(0.65 mole) diethylenetriamine and 6.9 grams of (0.05 mole) potash solids, 142.0 grams are slowly instilled under stirring, and (0.5 rubs
You) ethyl palmitate, reacts 4 hours in 120~160 DEG C of reaction temperature, is collected simultaneously the ethyl alcohol that reaction generates, institute can be obtained
The amide compound C needed15H31CO(NHCH2CH2)2NH2, yield 94.5%.
B, reflux condensing tube will be housed, dropping funel is added after water removal in the three-necked flask device of thermometer is clean
LiAlH(OEt)351 grams (0.3 moles) and 120 milliliters of anhydrous ethers, are stirred, and are added dropwise at -5~5 DEG C and contain 34.1 gram (0.1
Mole) C15H31CO(NHCH2CH2)2NH250wt% anhydrous ether solution, drip that be slowly warming up to 30 DEG C or so reactions 5 small
When.Reaction solution is carefully poured into ice water, it is post-treated to obtain long-chain polyamines compound C15H31CH2(NHCH2CH2)2NH2, yield
83.4%.
C, 130.8 grams of (0.4 mole) C are added into the pressure reactor equipped with agitating device15H31CH2(NHCH2CH2)2NH2, 5.2 grams of potassium carbonate, successively with 70.8 grams of (1.22 moles) propylene oxide, 35.2 grams of (0.8 mole) ethylene oxide 140~
160 DEG C of reactions obtain 2 (R of long-chain polyamines polyether compound1=C16H33, m=2, s1+s2+2s3=3, r1+r2+2r3=2, R2=
R3=R4=H), yield 97.6%.
D, 2 (R of long-chain polyamines polyether compound1=C16H33, m=2, s1+s2+2s3=3, r1+r2+2r3=2, R2=R3
=R4=H) 58.9 grams (0.1 moles) and 5.7 grams of (0.11 mole) sodium methoxides, 13.4 grams (0.11 mole of third sultone of 1,3- and
100 milliliters of cyclopentanone are mixed in the four-hole boiling flask equipped with mechanical stirring, thermometer and reflux condensing tube, are warming up to back after adding
Stream reaction 5 hours.Solvent is evaporated off, ammonium hydroxide is added, obtains 2 (R of long-chain polyamines polyether compound1=C16H33, m=2, s1+s2+2s3
=3, r1+r2+2r3=2) propane sulfonic acid ammonium (R2、R3、R4One of them is CH2CH2CH2SO3NH4, remaining is H).
E, by 2 (R of long-chain polyamines polyether compound1=C16H33, m=2, s1+s2+2s3=3, r1+r2+2r3=2) third
Ichthyodin 80g, C16H33OC2H4N+(CH3)2CH2COO-It 20 grams, is uniformly mixed after adding water, the foaming water discharge agent of 40% content is made
FM04。
(2) with [embodiment 1], the difference is that aging 72 hours at 150 DEG C, the results are shown in Table shown in 5.
[embodiment 6]
With [embodiment 5], pH is adjusted to 7 and 4 simulation neutrality and acidity when measuring FM04 performance, with hydrochloric acid by difference
Gaseous environment, aging 72 hours, the results are shown in Table shown in 6 at 150 DEG C.
[embodiment 7]
(1) preparation of foam discharging agent FM05:
A, 36.0 grams are added in the reaction flask of Xiang Peiyou mechanical stirring, thermometer, dropping funel and atmospheric distillation plant
(0.6 mole) ethylenediamine and 13.8 grams of (0.1 mole) potash solids, slowly instill 177.0 grams of (0.5 moles) 20 under stirring
Carbomethoxyphenyl reacts 3 hours in 120~160 DEG C of reaction temperature, is collected simultaneously the methanol that reaction generates, can be obtained required
Amide compound C21H43CONHCH2CH2NH2, yield 91.6%.
B, reflux condensing tube will be housed, dropping funel is added after water removal in the three-necked flask device of thermometer is clean
15.2 grams of lithium aluminium hydride reduction (0.4 mole) and 100 milliliters of dry dioxane, are dispersed with stirring mixing, contain in -10~5 DEG C of dropwise additions
38.2 grams of (0.1 mole) C21H43CONHCH2CH2NH240wt% dioxane solution, drip and be slowly warming up to 35 DEG C or so
Reaction 3 hours.Reaction solution is carefully poured into ice water, it is post-treated to obtain long-chain polyamines compound C21H43CH2NHCH2CH2NH2,
Yield 87.9%.
C, 147.2 grams of (0.4 mole) C are added into the pressure reactor equipped with agitating device21H43CH2NHCH2CH2NH2、
5.2 grams of potassium carbonate react to obtain long-chain polyamines polyether compound at 140~160 DEG C with 280.7 grams of (4.84 moles) propylene oxide
3(R1=C22H45, m=1, s1+s2+s3=12, r1+r2+r3=0, R2=R3=R4=H), yield 98.1%.
D, 3 (R of long-chain polyamines polyether compound1=C22H45, m=1, s1+s2+s3=12, r1+r2+r3=0, R2=R3=
R4=H) 106.4 grams (0.1 moles) and 16.8 grams of (0.3 mole) potassium hydroxide, 15.9 grams of (0.12 mole) potassium chloroacetates and 400
Milliliter acetone is mixed in the reaction kettle equipped with mechanical stirring, thermometer and reflux condensing tube, is heated to back flow reaction 10 hours.
Solvent is evaporated off, obtains 3 (R of long-chain polyamines polyether compound1=C22H45, m=1, s1+s2+s3=12, r1+r2+r3=0) second
Sour potassium (R2、R3、R4One of them is CH2COOK, remaining is H).
E, by 3 (R of long-chain polyamines polyether compound1=C22H45, m=1, s1+s2+s3=12, r1+r2+r3=0) acetic acid
Potassium (R2、R3、R4One of them is CH2COOK, remaining is H) 15 grams, C22H45OC2H4N+(CH2CH2OH)2(CH3)CH2COO-90 grams,
Internal olefin sulphonates IOS (C19~23) 30 grams, it is uniformly mixed after adding water, the foaming water discharge agent FM05 of 35% content is made.
(2) with [embodiment 1], the difference is that aging 24 hours at 200 DEG C, the results are shown in Table shown in 7.
[embodiment 8]
With [embodiment 7], pH is adjusted to 7 and 4 simulation neutrality and acidity when measuring FM05 performance, with hydrochloric acid by difference
Gaseous environment, aging 24 hours, the results are shown in Table shown in 8 at 200 DEG C.
[embodiment 9]
(1) preparation of foam discharging agent FM06:
A, 36.0 grams are added in the reaction flask of Xiang Peiyou mechanical stirring, thermometer, dropping funel and atmospheric distillation plant
(0.6 mole) ethylenediamine and 13.8 grams of (0.1 mole) potash solids, slowly instill 158.3 grams of (0.5 mole) rosin under stirring
Sour methyl esters (formula 3) is reacted 8 hours in 120~160 DEG C of reaction temperature, is collected simultaneously the methanol that reaction generates, can be obtained required
Amide compound C19H29CONHCH2CH2NH2, yield 85.6%.
B, reflux condensing tube will be housed, dropping funel is added after water removal in the three-necked flask device of thermometer is clean
13.3 grams of lithium aluminium hydride reduction (0.35 mole) and 100 milliliters of dry dioxane, are dispersed with stirring mixing, contain in -10~5 DEG C of dropwise additions
34.4 grams of (0.1 mole) C19H29CONHCH2CH2NH240wt% dioxane solution, drip and be slowly warming up to 35 DEG C or so
Reaction 5 hours.Reaction solution is carefully poured into ice water, it is post-treated to obtain rosin polyamine compounds C19H29CH2NHCH2CH2NH2,
Yield 73.2%.
C, 132.0 grams of (0.4 mole) C are added into the pressure reactor equipped with agitating device19H29CH2NHCH2CH2NH2、
5.0 grams of potassium hydroxide react to obtain rosin polyamines polyethers chemical combination at 140~160 DEG C with 160.2 grams of (3.64 moles) ethylene oxide
4 (R of object1=C20H31, m=1, s1+s2+s3=0, r1+r2+r3=9, R2=R3=R4=H), yield 91.4%.
D, 4 (R of rosin polyamines polyether compound1=C20H31, m=1, s1+s2+s3=0, r1+r2+r3=9, R2=R3=R4
=H) 72.6 grams (0.1 moles) and 8.0 grams of (0.2 mole) sodium hydroxides, 33.3 grams of (0.2 mole) 2- chloroethene sodium sulfonates and 100
Milliliter toluene is mixed in the reaction kettle equipped with mechanical stirring, thermometer and reflux condensing tube, is heated to back flow reaction 6 hours.
Solvent is evaporated off, obtains 4 (R of long-chain polyamines polyether compound1=C20H31, m=1, s1+s2+s3=0, r1+r2+r3=9) second sulphur
Sour sodium (R2、R3、R4One of them is CH2CH2SO3Na, remaining is H).
E, by 4 (R of long-chain polyamines polyether compound1=C20H31, m=1, s1+s2+s3=0, r1+r2+r3=9) second sulphur
Sour sodium (R2、R3、R4One of them is CH2CH2SO3Na, remaining is H) 90 grams, C18H37O(C2H4O)2C2H4N+(CH3)2CH2COO-5
Gram, a- alkene sulfonate AOS (C14~18) 5 grams, it is uniformly mixed after adding water, the foaming water discharge agent FM06 of 30% content is made.
(2) it with [embodiment 1], the results are shown in Table shown in 9.
[embodiment 10]
With [embodiment 9], pH is adjusted to the high acid gas-containing of 2 simulations when measuring FM06 performance, with hydrochloric acid by difference
Environment the results are shown in Table shown in 10.
[embodiment 11]
With [embodiment 10], the difference is that by 4 (R of long-chain polyamines polyether compound1=C20H31, m=1, s1+s2+s3
=0, r1+r2+r3=9) ethanesulfonic acid sodium (R2、R3、R4One of them is CH2CH2SO3Na, remaining is H) 30 grams,
C16H33C6H4SO390 grams of Na (cetyl benzenesulfonic acid sodium) is uniformly mixed after adding water, the foaming water discharge agent of 30% content is made
FM07 the results are shown in Table shown in 11.
[embodiment 12]
With [embodiment 1], the difference is that the kerosene of certain mass score is added, the results are shown in Table shown in 12 before aging.
[embodiment 13]
With [embodiment 2], the difference is that being passed through in gas acid containing hydrogen sulfide and carbon dioxide when surveying liquid carry over
Gas the results are shown in Table shown in 13.
[comparative example 1]
With [embodiment 1], the difference is that respectively with 1 (R of long-chain polyamines polyether compound1=C18H35, m=5, s1+s2
+ 5s3=20, r1+r2+5r3=3) hydroxypropionate sodium (R2、R3、R4One of them is CH2CH(OH)CH2SO3Na, remaining is
H) 100 grams, C16H33OC2H4N+(CH3)3Br-100 grams, C16H33SO3K100 grams of substitution " 1 (R of long-chain polyamines polyether compound1=
C18H35, m=5, s1+s2+5s3=20, r1+r2+5r3=3) hydroxypropionate sodium (R2、R3、R4One of them is CH2CH
(OH)CH2SO3Na, remaining is H) 50 grams, C16H33OC2H4N+(CH3)3Br-40 grams, C16H33SO310 grams of K " forms foaming water discharge
Agent FM08, FM09 and FM10, simulation water are 100,000mg/LNaCl, be the results are shown in Table shown in 14.
[comparative example 2]
With [embodiment 5], the difference is that respectively with 2 (R of long-chain polyamines polyether compound1=C16H33, m=2, s1+s2
+ 2s3=3, r1+r2+2r3=2) 100 grams of propane sulfonic acid ammonium, C16H33OC2H4N+(CH3)2CH2COO-100 grams of substitution " long-chain polyamines
2 (R of polyether compound1=C16H33, m=2, s1+s2+2s3=3, r1+r2+2r3=2) propane sulfonic acid ammonium 80g, C16H33OC2H4N+
(CH3)2CH2COO-20 grams ", foaming water discharge agent FM11 and FM12 are formed, simulation water is 100,000mg/LNaCl, the results are shown in Table 15
It is shown.
[comparative example 3]
With [embodiment 7], the difference is that with 3 (R of long-chain polyamines polyether compound1=C22H45, m=1, s1+s2+s3
=12, r1+r2+r3=0) potassium acetate (R2、R3、R4One of them is CH2COOK, remaining is H) 135 grams of substitution " long-chain polyamines
3 (R of polyether compound1=C22H45, m=1, s1+s2+s3=12, r1+r2+r3=0) potassium acetate (R2、R3、R4One of them is
CH2COOK, remaining is H) 15 grams, C22H45OC2H4N+(CH2CH2OH)2(CH3)CH2COO-90 grams, internal olefin sulphonates IOS
(C19~23) 30 grams ", foaming water discharge agent FM13 is formed, simulation water is 100,000mg/LNaCl, be the results are shown in Table shown in 15.
[comparative example 4]
With [embodiment 9], the difference is that with 4 (R of long-chain polyamines polyether compound1=C20H31, m=1, s1+s2+s3
=0, r1+r2+r3=9) ethanesulfonic acid sodium (R2、R3、R4One of them is CH2CH2SO3Na, remaining is H) 100 grams of substitution " long-chains
4 (R of polyamines polyether compound1=C20H31, m=1, s1+s2+s3=0, r1+r2+r3=9) ethanesulfonic acid sodium (R2、R3、R4Wherein
One of be CH2CH2SO3Na, remaining is H) 90 grams, C18H37O(C2H4O)2C2H4N+(CH3)2CH2COO-5 grams, a- alkene sulfonate
AOS(C14~18) 5 grams ", foaming water discharge agent FM14 is formed, simulation water is 100,000mg/LNaCl, be the results are shown in Table shown in 15.
[comparative example 5]
With [embodiment 1], the difference is that with " C17H33CO(NHCH2CH2)5NH250 grams, C16H33OC2H4N+(CH3)3Br-40 grams, C16H33SO310 grams of K " substitution " long-chain polyamines polyether compound1(R1=C18H35, m=5, s1+s2+5s3=20,
R1+r2+5r3=3 hydroxypropionate sodium (R)2、R3、R4One of them is CH2CH(OH)CH2SO3Na, remaining is H) 50 grams,
C16H33OC2H4N+(CH3)3Br-40 grams, C16H33SO310 grams of K ", forms foaming water discharge agent FM15, and simulation water is 100,000mg/
LNaCl the results are shown in Table shown in 16.
[comparative example 6]
With [comparative example 5], the difference is that pH is adjusted to 7 and 4 simulation neutrality and acid with hydrochloric acid when measurement FM15 performance
Property gaseous environment, the results are shown in Table shown in 17.
[comparative example 7]
With [embodiment 9], the difference is that with " C19H29CONHCH2CH2NH290 grams, C18H37O(C2H4O)2C2H4N+
(CH3)2CH2COO-5 grams, a- alkene sulfonate AOS (C14~18) 5 grams " substitution " 4 (R of long-chain polyamines polyether compound1=C20H31, m
=1, s1+s2+s3=0, r1+r2+r3=9) ethanesulfonic acid sodium (R2、R3、R4One of them is CH2CH2SO3Na, remaining is H) 90
Gram, C18H37O(C2H4O)2C2H4N+(CH3)2CH2COO-5 grams, a- alkene sulfonate AOS (C14~18) 5 grams ", form foaming water discharge agent
FM16, simulation water are 100,000mg/LNaCl, be the results are shown in Table shown in 16.
[comparative example 8]
With [comparative example 7], the difference is that pH is adjusted to 2 simulation height containing sour gas with hydrochloric acid when measurement FM16 performance
Body environment, the results are shown in Table shown in 17.
Table 1
Table 2
Table 3
Table 4
Table 5
Table 6
Table 7
Table 8
Table 9
Table 10
Table 11
Table 12
Table 13
Table 14
Table 15
Table 16
Table 17
Claims (10)
1. a kind of method that ultra-deep gas well uses the water pumping gas production of foaming water discharge agent composition, comprising the following steps:
(1) foaming water discharge agent composition and water are mixed to get foaming water discharge agent composition solution;
(2) foaming water discharge agent composition solution or foaming water discharge agent composition solution and the mixed solution of oil are sufficiently connect with gas
Touching, formed aerated fluid, by the foaming water discharge agent composition solution water or oil water mixture displacement come out;
Wherein, the foaming water discharge agent composition, in terms of mass fraction, including following components:
1) 1 part of polyamines polyether compound;
2) 0.01~100 portion of cosurfactant;
Wherein, the polyamines polyether compound is with general molecular formula shown in formula (1):
In formula (1), R1Selected from C4~C32One of alkyl or substituted hydrocarbon radical, R2、R3、R4It is independently selected from H, C1~C5Hydrocarbon carboxylic acids
Salt or substituted hydrocarbon radical carboxylate, C1~C5Hydrocarbyl sulfonate or substituted hydrocarbyl sulfonic acid salt, C1~C5Hydrocarbyl phosphate salt or substituted hydrocarbon radical
Phosphate and C1~C5At least one of sulfovinic acid ester salt or substituted hydrocarbon radical sulfuric acid, and be not simultaneously H;M is-N (A)
CH2CH2The number of segment, m=1~10;A is substituent group shown in formula (4);S1, s2, s3 are the adduction number that propoxyl group rolls into a ball PO,
S1=0~30, s2=0~30, s3=0~30;R1, r2, r3 be ethoxy group EO adduction number, r1=0~30, r2=0~
30, r3=0~30, and s1+s2+m*s3 and r1+r2+m*r3 are not zero simultaneously;
The gas is at least one of air, nitrogen, methane or natural gas, can contain or not contain H2S or CO2It is acid
Gas;The oil is at least one of kerosene, crude oil or condensate.
2. the method that ultra-deep gas well according to claim 1 uses the water pumping gas production of foaming water discharge agent composition, feature exist
In the cosurfactant in amphoteric ion or cationic surfactant, anionic surfactant at least one
Kind;The amphoteric ion or cationic surfactant have general molecular formula shown in formula (2):
In formula (2), R5For selected from C4~C32One of alkyl or substituted hydrocarbon radical, R6、R7It is independently selected from (CH2)aOH、(CH2)bCH3
Or C6H5CH2One of, R8Selected from (CH2)aOH、(CH2)bCH3、C6H5CH2、(CH2)cOr (CH2)c(CHOH)d(CH2)eIn
One kind, any integer in a=2~4, any integer in b=0~5, any integer in c=1~4, in d=0~3
Any integer, any integer in e=1~4;N is the adduction number that propoxyl group rolls into a ball PO, n=0~15;P is adding for ethoxy group EO
Close number, p=0~30;X-For selected from OH-, halogen anion, HCO3 -、NO3 -、CH3OSO3 -、CH3COO-、COO-、SO3 -Or OSO3 -
One of;
The anionic surfactant has general molecular formula shown in formula (3):
In formula (3), R9With R10The sum of for selected from C3~C31One of alkyl or substituted hydrocarbon radical, M be selected from hydrogen, alkali metal or by
Formula NR11(R12)(R13)(R14) shown at least one of group, R11、R12、R13、R14To be independently selected from H, (CH2)aOH or
(CH2)bCH3One of, any integer in a=2~4, b=0~5.
3. the method that ultra-deep gas well according to claim 2 uses the water pumping gas production of foaming water discharge agent composition, feature exist
In the R1、R5For C8~C24Alkyl or substituted hydrocarbon radical;R9With R10The sum of be C7~C23Alkyl or substituted hydrocarbon radical;R2、R3、R4It is independent
Selected from H, CH2COOM1、(CH2)3SO3M1Or CH2(CHOH)CH2SO3M1One of, and be not simultaneously H, the M1For hydrogen, alkali gold
Belong to or by formula NR11(R12)(R13)(R14) shown at least one of group, R11、R12、R13、R14It is independently selected from H, (CH2)aOH
Or (CH2)bCH3One of, any integer in a=2~4, b=0~5;R6、R7For CH3、C2H5、(CH2)2OH or C6H5CH2
One of;R8For CH3、C2H5、(CH2)2OH or C6H5CH2One of or R8X-For CH2COO-、(CH2)3SO3 -、CH2(CHOH)
CH2SO3 -One of.
4. the method that ultra-deep gas well according to claim 2 uses the water pumping gas production of foaming water discharge agent composition, feature exist
In m=1~5;S1+s2+m*s3=0~5, r1+r2+m*r3=0~10, and s1+s2+m*s3 and r1+r2+m*r3 difference
When be zero;N=0~5, p=0~5.
5. the method that ultra-deep gas well according to claim 1 uses the water pumping gas production of foaming water discharge agent composition, feature exist
In it is described bubble drain combination object in polyamines polyether compound, cosurfactant mass ratio be 1: (0.1~10).
6. the method that any ultra-deep gas well uses the water pumping gas production of foaming water discharge agent composition according to claim 1~5,
It is characterized in that the preparation method of the foaming water discharge agent composition, comprising the following steps:
(1) preparation of polyamines polyether compound
A, amidation process:
By R0COOR ' and H (NHCH2CH2)mNH2, catalyst is with molar ratio 1:(1~2): (0~0.5) mixing, in reaction under stirring
50~200 DEG C of temperature are reacted 3~15 hours, and alcohol or water that reaction generates are evaporated off under normal pressure or reduced pressure, institute can be obtained
The amide compound R needed0CO(NHCH2CH2)mNH2;Wherein, R0Selected from C3~C31One of alkyl or substituted hydrocarbon radical, R ' are selected from
H, it is selected from C1~C8Alkyl, c=1~10, catalyst is in alkali metal hydroxide, alkali metal alcoholates, alkali carbonate
At least one;
B, reduction reaction:
R0CO(NHCH2CH2)mNH2The method that the reduction of middle amide uses catalytic hydrogenation, occurs heterogeneous catalysis at high temperature under high pressure
Reaction generates corresponding amine, or uses: the R that step a is synthesized0CO(NHCH2CH2)mNH2With metal hydride H-Y+Non-proton
Reduction reaction is carried out in type solvent, obtains R0CH2(NHCH2CH2)mNH2;Wherein, Y+For metallic compound, metal alkyl chemical combination
Object, metal amide.
C, poly- etherification reaction:
In the presence of basic catalyst, R that step b is synthesized0CH2(NHCH2CH2)cNH2Successively with aequum propylene oxide, ring
Oxidative ethane reacts to obtain long-chain polyamines polyethers intermediate product R0CH2{N[(CHCH3CH2O)s3(CH2CH2O)r3H][CH2CH2]}mN
[(CHCH3CH2O)s1(CH2CH2O)r1H][CHCH3CH2O)s2(CH2CH2O)r2)H];
D, carboxylation or sulfonating reaction:
The long-chain polyamines polyethers intermediate product and ionization reagent and alkali that step c is obtained are with molar ratio 1:(1~5): (1~10)
In a solvent, it reacts to generate for 3~20 hours in 50~120 DEG C of reaction temperature and there is polyamines polyether carboxylic acid shown in structural formula (1)
Salt or polyamines polyether sulfonate;The ionization reagent is selected from XR15Y1Or XR '15Y′1At least one of;The alkali choosing
From alkali metal hydroxide or alkali metal alcoholates;Y1With Y '1For SO3M1Or COON1, M1And N1For alkali metal, X is chlorine, bromine or iodine;
(2) the polyamines polyether compound of step (1) synthesis, cosurfactant are uniformly mixed according to required mass fraction,
The foaming water discharge agent composition is made.
7. the method that ultra-deep gas well according to claim 6 uses the water pumping gas production of foaming water discharge agent composition, feature exist
The R described in step a0COOR’、H(NHCH2CH2)mNH2, catalyst molar ratio 1:(1~1.3): (0~0.1), catalyst are hydrogen
At least one of sodium oxide molybdena, potassium hydroxide, sodium carbonate, potassium carbonate.
8. the method that ultra-deep gas well according to claim 6 uses the water pumping gas production of foaming water discharge agent composition, feature exist
The H described in step b-Y+For LiAlH4、LiAlH(OEt)3Or NaBH4At least one of, aprotic solvents are ether, tetrahydro
At least one of furans, dioxane;Long-chain polyamines polyethers intermediate product described in step d: ionization reagent: mole of alkali
Than being 1: (1~2): (1~4;The solvent is selected from C3~C8Ketone and C6~C9At least one of aromatic hydrocarbons.
9. the method that ultra-deep gas well according to claim 1 uses the water pumping gas production of foaming water discharge agent composition, feature exist
In the gas be at least one of nitrogen, methane or natural gas, H2S and CO2Content be 15~35%;The oil is coal
At least one of oil or condensate.
10. the method that any ultra-deep gas well uses the water pumping gas production of foaming water discharge agent composition according to claim 1~5,
It is characterized in that the ultra-deep gas well formation temperature is 150~200 DEG C, 5000~200000mg/ of total salinity of formation brine
L, H2S and CO2Content 0~35%.
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