CN109679637A - The method that ultra-deep gas well uses the composition water pumping gas production of solid foam water discharge agent - Google Patents
The method that ultra-deep gas well uses the composition water pumping gas production of solid foam water discharge agent Download PDFInfo
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- 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
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
- C08G65/2621—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
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- 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
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Abstract
The present invention relates to the methods that ultra-deep gas well uses the composition water pumping gas production of solid foam water discharge agent, mainly solve existing foaming water discharge agent containing H2S、CO2Resisting high temperature, high salt performance is poor under acidic environment, can not solve high temperature and high salt ultra-deep gas well because of the underproduction even stop-spraying caused by hydrops and liquid foam discharging agent filling difficult problem.1) present invention is by using the following steps are included: be mixed to get foaming water discharge agent solution for solid foam water discharge agent composition and water；2) foaming water discharge agent solution or foaming water discharge agent solution and the mixed solution of oil are come into full contact with gas, forms aerated fluid, water or oil water mixture displacement is come out；Solid foam discharging agent composition includes: the technical solution of polyamines polyether compound shown in 1 part of formula (1), 0.01~100 portion of cosurfactant, 0.05~1000 part of solid filler, 0~0.5 part of binder, the problem is preferably resolved, 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 composition water pumping gas production of solid foam water discharge agent.
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
Solve the problems, such as high temperature ultra-deep gas well because caused by hydrops the underproduction even stop-spraying and the filling of liquid foam water discharge agent it is difficult, mention
For a kind of method that ultra-deep gas well uses the composition water pumping gas production of solid foam water discharge agent, it is applied to high temperature deep well, in acid item
There is very good heat resistance under part, have and take liquid, blistering and foam stability energy by force.
In order to solve the above technical problems, The technical solution adopted by the invention is as follows: a kind of ultra-deep gas well uses solid foam
The method of water discharge agent composition water pumping gas production, comprising the following steps:
(1) solid foam water discharge agent composition and water are mixed to get foaming water discharge agent solution；
(2) foaming water discharge agent solution or foaming water discharge agent solution and the mixed solution of oil are come into full contact with gas, is formed
Aerated fluid, by the foaming water discharge agent solution water or oil water mixture displacement come out；
Wherein, the solid foam 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；
3) 0.05~1000 part of solid filler；
4) 0~0.5 part of binder；
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 or 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 (3)；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 preferably be selected from amphoteric ion or cationic surfactant, yin from
At least one of sub- surfactant；The amphoteric ion or cationic surfactant preferably have molecule shown in formula (2)
General formula:
In formula (2), R5For selected from C4~C32One of alkyl or substituted hydrocarbon radical, R6、R7It is independently selected from (CH2)aOH、
(CH2)bCH3Or C6H5CH2One of, R8Selected from (CH2)aOH、(CH2)bCH3、C6H5CH2、(CH2)cOr (CH2)c(CHOH)d
(CH2)eOne of, any integer in a=2~4, any integer in b=0~5, any integer in c=1~4, d=
Any integer in 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 ethyoxyl
The adduction number of 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 C3~C31One 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, the solid filler is carbonate, bicarbonate, sulfate, phosphate, borate, gold
Belong to halide, formates, acetate, tartaric acid and salt, citric acid and salt, phthalic acid and salt, gallic acid and salt, urine
At least one of element, biuret etc.；Binder is dextrin, epoxy resin, polyacrylamide, starch, cellulose, polyethylene glycol
At least one of Deng.
In above-mentioned technical proposal, R1、R5Preferably C8~C24Alkyl or substituted hydrocarbon radical.In above-mentioned technical proposal, R2、R3、R4
Independent 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、R14Preferably 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, solid packing is preferably sodium carbonate, sodium bicarbonate, Boratex, sodium chloride, sodium acetate, wine
At least one of stone acid, sodium tartrate, citric acid, sodium citrate, phthalic acid potassium, urea, biuret.
In above-mentioned technical proposal, binder is preferably at least one of polyacrylamide, starch, polyethylene glycol.
In above-mentioned technical proposal, polyamines polyether compound in solid foam water discharge agent, cosurfactant, solid filler with
The mass ratio of binder is 1: (0.1~10): (0.1~200): (0.01~0.1).
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.
Solid foam discharging agent composition key active ingredient of the present invention is (1) and (2), can be by the polyamines polyether compound
It is obtained by mixing with the solid packing and binder in required ratio, is preferably obtained with following preferred technical solutions.
In above-mentioned technical proposal, the preparation method of the solid foam water discharge agent composition preferably includes 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)mNH2.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, the polyamines polyether compound, cosurfactant, solid of step (1) synthesis are filled out
Material and binder are uniformly mixed, and are then pressed into type, and the solid foam water discharge agent composition is made.
In above-mentioned technical proposal, the shape of the solid foam water discharge agent composition can be the shapes such as stick or ball.
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 solid foam water discharge agent composition that the present invention is suitable for ultra-deep gas well has good compatibility, can also contain
Other inorganic agents commonly used in the art.
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 exactly this method using solid foam water discharge agent water pumping gas production suitable for ultra-deep gas well.
The thermal decomposition temperature of polyamines polyether compound prepared by the present invention is at 200 DEG C or more, in acidic aqueous solution not
Hydrolysis or very micro hydrolysis have good heat resistance；On the one hand non-ionic segment and more hydrophilic groups in molecule increase
Add salt-resistance, the amount of the combination water and irreducible water that carry foaming agent increases, and foam carrier amount enhancing, analysis liquid subtracts
Slowly；Secondly, increasing foaming agent in the suction of gas-liquid interface simultaneous with the functional group of yin, yang opposite-sign in foaming water discharge agent
The composition of attached amount, formation is more efficient；In addition, being made it possible to containing the hetero atom responded to pH lower dense in molecule
During degree is applied to 150 DEG C or more of acidic high-temperature ultradeep well water pumping gas production with high salt.
Foam discharging agent key active principle and solid packing, binder have good compatibility, form solid composite not
Influence its foaming water discharge performance.
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 high temperature ageing, foam height reaches 175mm, takes liquid rate up to 93.9%, has in acidic environment excellent
Heat-resistant salt-resistant, blister and take fluidity energy, achieve preferable technical effect.
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.
Below by embodiment, the present invention is further elaborated.
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 FMG01
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 long-chain polyamines polyether compound1(R1=C18H35, m=5, s1+s2+5s3=20, r1+r2+5r3=3,
R2=R3=R4=H), yield 96.2%.
D, long-chain polyamines polyether compound1(R1=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 long-chain polyamines polyether compound1(R1=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 long-chain polyamines polyether compound1(R1=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, C16H33SO310 grams of K, 100 grams of sodium tartrate, 90 grams of sodium chloride, 30 grams of urea be uniformly mixed, add 10% cellulose water-soluble
Rodlike, obtained foam drainage rod FMG01 is pressed into after 30 grams of liquid mixing.
(2) FMG01 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 FMG01, the results are shown in Table 1.
The nitrogen of 4000mL/min is continuously passed through foam discharging agent FMG01 aqueous solution, measures foamover in 15 minutes
Liquid rate is taken in water out, calculating, and the results are shown in Table 1.The liquid carry over measurement device of use is as shown in Figure 1.It is acidproof using pressure resistance
Aging equipment is tested, and after 180 DEG C of agings for 24 hours, redeterminates starting foaming height, after five minutes foaming height and 15 minutes
Take the performances such as liquid rate, the results are shown in Table 1.
[embodiment 2]
With [embodiment 1], difference when measure FMG01 performance, with hydrochloric acid by pH be adjusted to 7,4 and 2 simulation neutrality and
Sour gas environment, the results are shown in Table shown in 2.
[embodiment 3]
With [embodiment 1], the difference is that by long-chain polyamines polyether compound1(R1=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-50 grams, 100 grams of sodium sulphate, 50 grams of saleratus, 30 grams of Boratex, 30 grams of biuret mixing
Uniformly, add 30 grams of 5% dextrin in aqueous solution to be uniformly mixed, foam drainage rod FMG02 is made, the results are shown in Table shown in 3.
[embodiment 4]
With [embodiment 1], the difference is that by long-chain polyamines polyether compound1(R1=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, C16H33SO350 grams of Na, 100 grams of sodium tartrate, 90 grams of sodium chloride, 30 grams of urea be uniformly mixed, add 10% cellulose water-soluble
30 grams of liquid are uniformly mixed, and foam drainage rod FMG03 is made, the results are shown in Table shown in 4.
[embodiment 5]
(1) preparation of foam discharging agent FMG04:
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 long-chain polyamines polyether compound2(R1=C16H33, m=2, s1+s2+2s3=3, r1+r2+2r3=2, R2=
R3=R4=H), yield 97.6%.
D, long-chain polyamines polyether compound2(R1=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 long-chain polyamines polyether compound2(R1=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 long-chain polyamines polyether compound2(R1=C16H33, m=2, s1+s2+2s3=3, r1+r2+2r3=2) third
Ichthyodin 80g, C16H33OC2H4N+(CH3)2CH2COO-20 grams, 100 grams of potassium citrate, 60 grams of urea, 60 grams of biuret mixing it is equal
It is even, add 30 grams of 1% polyacrylamide solution to be uniformly mixed, foam drainage rod FMG04 is made.
(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 7,4 and 2 when measure FMG04 performance, with hydrochloric acid by difference, simulation it is neutral with
Sour gas 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 FMG05:
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 oxide3(R1=C22H45, m=1, s1+s2+s3=12, r1+r2+r3=0, R2=R3=R4=H), yield 98.1%.
D, long-chain polyamines polyether compound3(R1=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 long-chain polyamines polyether compound3(R1=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 long-chain polyamines polyether compound3(R1=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, 100 grams of sodium sulphate, 100 grams of sodium tartrate, 70 grams of potassium chloride be uniformly mixed, add
10% 60 grams of polyethylene glycol is uniformly mixed, and foam drainage rod FMG05 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 7,4 and 2 when measure FMG05 performance, with hydrochloric acid by difference, simulation it is neutral with
Sour gas 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 FMG06:
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
Object4(R1=C20H31, m=1, s1+s2+s3=0, r1+r2+r3=9, R2=R3=R4=H), yield 91.4%.
D, rosin polyamines polyether compound4(R1=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 long-chain polyamines polyether compound4(R1=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 long-chain polyamines polyether compound4(R1=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, 50 grams of phthalic acid potassium, 150 grams of biuret, add 5% polyglycol solution 30
Gram be uniformly mixed, be made foam drainage rod FMG06.
(2) it with [embodiment 1], the results are shown in Table shown in 9.
[embodiment 10]
With [embodiment 9], pH is adjusted to 7,4 and 2 when measure FMG06 performance, with hydrochloric acid by difference, simulation it is neutral with
Acid gas-containing environment, the results are shown in Table shown in 10.
[embodiment 11]
With [embodiment 10], the difference is that by long-chain polyamines polyether compound4(R1=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), 30 grams of potassium citrate, 50 grams of urea, 100 grams of potassium carbonate, sodium acetate
60 grams are uniformly mixed, and add 30 grams of 1% polyacrylamide solution to be uniformly mixed, foam drainage rod FMG07 is made, the results are shown in Table 11
It is shown.
[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 long-chain polyamines polyether compound1(R1=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 " long-chain polyamines polyether compound1(R1=
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 ", other additives are not
Become, form foam drainage rod FMG08, FMG09 and FMG10, simulation water is 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 long-chain polyamines polyether compound2(R1=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
Polyether compound2(R1=C16H33, m=2, s1+s2+2s3=3, r1+r2+2r3=2) propane sulfonic acid ammonium 80g, C16H33OC2H4N+
(CH3)2CH2COO-20 grams ", other additives are constant, form foam drainage rod FMG11 and FMG12, and simulation water is 100,
000mg/LNaCl the results are shown in Table shown in 15.
[comparative example 3]
With [embodiment 7], the difference is that with long-chain polyamines polyether compound3(R1=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
Polyether compound3(R1=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 ", other additives are constant, form foam drainage rod FMG13, and simulation water is 100,000mg/LNaCl, as a result
It is shown in Table 15.
[comparative example 4]
With [embodiment 9], the difference is that with long-chain polyamines polyether compound4(R1=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
Polyamines polyether compound4(R1=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 ", other additives are constant, form foam drainage rod FMG14, and simulation water is 100,000mg/LNaCl, knot
Fruit is shown in Table 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 ", other additives are constant, form foam drainage rod FMG15, mould
Quasi- water is 100,000mg/LNaCl, be the results are shown in Table shown in 16.
[comparative example 6]
With [comparative example 5], the difference is that when measurement FMG15 performance, with hydrochloric acid by pH be adjusted to 7 and 4 simulations it is neutral and
Sour gas 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 " long-chain polyamines polyether compound4(R1=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 ", other additives are not
Become, form foam drainage rod FMG16, simulation water is 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 FMG16 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 composition water pumping gas production of solid foam water discharge agent, comprising the following steps:
(1) solid foam water discharge agent composition and water are mixed to get foaming water discharge agent solution；
(2) foaming water discharge agent solution or foaming water discharge agent solution and the mixed solution of oil are come into full contact with gas, forms foam
Fluid, by the foaming water discharge agent solution water or oil water mixture displacement come out；
Wherein, the solid foam 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；
3) 0.05~1000 part of solid filler；
4) 0~0.5 part of binder；
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 or 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 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 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 composition water pumping gas production of solid foam water discharge agent, special
Sign is the cosurfactant in amphoteric ion or cationic surfactant, anionic surfactant at least
It is a kind of；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)c、(CH2)c(CHOH)d(CH2)eIn one
It plants, any integer in a=2~4, any integer in b=0~5, any integer in c=1~4, appointing in d=0~3
One 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 the adduction of ethoxy group EO
Number, p=0~30；X-For selected from OH-, halogen anion, HCO3 -、NO3 -、CH3OSO3 -、CH3COO-、COO-、SO3 -Or OSO3 -In
One kind；
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 composition water pumping gas production of solid foam water discharge agent, special
Sign is the R1、R5For C8~C24Alkyl or substituted hydrocarbon radical；R9With R10The sum of be C7~C23Alkyl or substituted hydrocarbon radical；R2、R3、R4
For H, CH2COOM1、(CH2)3SO3M1Or CH2(CHOH)CH2SO3M1One of, and be not simultaneously H；R6、R7For CH3、C2H5、
(CH2)2OH or C6H5CH2One of；R8For CH3、C2H5、(CH2)2OH or C6H5CH2One of or R8X-For CH2COO-、
(CH2)3SO3 -、CH2(CHOH)CH2SO3 -One of；M=1~5；S1+s2+m*s3=0~5, r1+r2+m*r3=0~10,
It and is not simultaneously zero；N=0~5, p=0~5.
4. solid foam water discharge agent composition according to claim 3, it is characterised in that the M1For 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.
5. the method that ultra-deep gas well according to claim 1 uses the composition water pumping gas production of solid foam water discharge agent, special
Sign is that the solid filler is carbonate, bicarbonate, sulfate, phosphate, borate, metal halide, formates, second
In hydrochlorate, tartaric acid and salt, citric acid and salt, phthalic acid and salt, gallic acid and salt, urea, biuret etc. at least
It is a kind of.
6. the method that ultra-deep gas well according to claim 1 uses the composition water pumping gas production of solid foam water discharge agent, special
Sign is that the mass ratio of the polyamines polyether compound, cosurfactant, solid filler and binder is 1: (0.1~10):
(0.1~200): (0.01~0.1).
7. any ultra-deep gas well uses the side of solid foam water discharge agent composition water pumping gas production according to claim 1~6
Method, it is characterised in that the preparation method of the solid foam 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)mNH2Successively 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 X R '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) according to required mass fraction, by the polyamines polyether compound of step (1) synthesis, cosurfactant, solid packing and
Binder is uniformly mixed, and is then pressed into type, and the solid foam water discharge agent composition is made.
8. the method that ultra-deep gas well according to claim 7 uses the composition water pumping gas production of solid foam water discharge agent, special
Sign is R described in step a0COOR’、H(NHCH2CH2)mNH2, catalyst molar ratio 1:(1~1.3): (0~0.1), catalyst
For at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate；H described in step b-Y+For LiAlH4、LiAlH
(OEt)3Or NaBH4One of, aprotic solvents are at least one of ether, tetrahydrofuran, dioxane；Step d institute
The long-chain polyamines polyethers intermediate product stated: ionization reagent: the molar ratio of alkali is 1: (1~2): (1~4；The solvent is selected from
C3~C8Ketone and C6~C9At least one of aromatic hydrocarbons；Long-chain polyamines polyethers intermediate product described in step d: ionization examination
Agent: the molar ratio of alkali is 1: (1~2): (1~4；The solvent is selected from C3~C8Ketone and C6~C9Aromatic hydrocarbons at least one
Kind.
9. the method that ultra-deep gas well according to claim 1 uses the composition water pumping gas production of solid foam water discharge agent, special
Sign is that the gas is at least one of nitrogen, methane or natural gas, H2S and CO2Content be 15~35%；The oil
For at least one of kerosene or condensate.
10. according to the method that any ultra-deep gas well of claim 5 uses the composition water pumping gas production of solid foam water discharge agent,
It is characterized in that the solid packing be sodium carbonate, sodium bicarbonate, Boratex, sodium chloride, sodium acetate, tartaric acid, sodium tartrate,
At least one of citric acid, sodium citrate, phthalic acid potassium, urea, biuret；The binder be polyacrylamide,
At least one of starch, polyethylene glycol.
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| CN115141343A (en) * | 2022-09-05 | 2022-10-04 | 万华化学集团股份有限公司 | Composition, adhesive composite material thereof, artificial board without aldehyde addition and preparation method thereof |
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| CN115141343A (en) * | 2022-09-05 | 2022-10-04 | 万华化学集团股份有限公司 | Composition, adhesive composite material thereof, artificial board without aldehyde addition and preparation method thereof |
| CN115141343B (en) * | 2022-09-05 | 2023-01-13 | 万华化学集团股份有限公司 | Composition, adhesive composition material thereof, aldehyde-free artificial board and preparation method thereof |
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