CN109679621A - Resisting high temperature, high salt solid foam water discharge agent and preparation method and application - Google Patents
Resisting high temperature, high salt solid foam water discharge agent and preparation method and application Download PDFInfo
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Abstract
The present invention relates to resisting high temperature, high salt solid foam water discharge agent and preparation method and applications, mainly solve existing foaming water discharge agent containing H2S、CO2Resisting high temperature, high salt performance is poor under acidic environment, can not solve the problems, such as high temperature and high salt ultra-deep gas well because caused by hydrops the underproduction even stop-spraying and the filling of liquid foam discharging agent it is difficult.The present invention by using in terms of mass fraction including following components: 1) 1 part of polyamine surfactant；2) 0.01~100 portion of cosurfactant；3) 0.05~1000 part of solid filler；4) 0~0.5 part of binder；Wherein the polyamine surfactant have formula 1) shown in general molecular formula；The cosurfactant has formula 2) shown in general molecular formula or formula 3) shown at least one of general molecular formula technical solution, preferably resolve 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 solid foam water discharge agent and preparation method and application, especially a kind of resisting high temperature, high salt solid
Foaming water discharge agent and preparation method and application.
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 to restrict high temperature ultra-deep gas well foaming water discharge technology under acid condition
The principal element of development.
Summary of the invention
The first technical problem to be solved by the present invention is that existing foaming water discharge agent high temperature resistance 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 discharging agent it is difficult, provide
A kind of resisting high temperature, high salt solid foam water discharge agent is applied to high temperature deep well, has very good temperature tolerance in acid condition
Can, have and takes liquid, blistering and foam stability energy by force.
The second technical problem to be solved by the present invention is corresponding to provide a kind of one of and solution above-mentioned technical problem
The preparation method of resisting high temperature, high salt solid foam water discharge agent.
The third technical problem to be solved by the present invention is corresponding to provide a kind of one of and solution above-mentioned technical problem
The application of resisting high temperature, high salt solid foam water discharge agent.
One of to solve above-mentioned technical problem, The technical solution adopted by the invention is as follows: solid foam water discharge agent, with quality
Number meter, including following components:
1) 1 part of polyamine surfactant；
2) 0.01~100 portion of cosurfactant；
3) 0.05~1000 part of solid filler；
4) 0~0.5 part of binder；
Wherein, the polyamine surfactant general molecular formula is shown in formula (1):
In formula (1), R1Selected from C4~C32One of alkyl or substituted hydrocarbon radical, R2、R3、R4It is independently selected from C1~C5Alkyl or
Substituted hydrocarbon radical, R5、R6It is independently selected from (CH2)cOr (CH2)c(CHOH)d(CH2)eOne of, any integer in c=1~4, d
Any integer in=0~3, any integer in e=1~4；Y1、Y2It is independently selected from COO-、SO3 -、OSO3 -One of；M is
Vinylamine substrate section number, any integer in m=1~10；T1, t2 are positive changes, and s1, s2 are respectively R5Y1、R6Y2Replace
Base number, t1=s1=0 or 1, t2=s2=0 or 1.
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), R7For selected from C4~C32One of alkyl or substituted hydrocarbon radical, R8、R9It is independently selected from (CH2)aOH、
(CH2)bCH3Or C6H5CH2One of, R10Selected 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 has general molecular formula shown in formula (3):
In formula (3), R11With R12The sum of for selected from C3~C31One of alkyl or substituted hydrocarbon radical, M are selected from hydrogen, alkali metal
Or by formula NR13(R14)(R15)(R16) shown at least one of group, R13、R14、R15、R16To 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、R7Independent is preferably C8~C24Alkyl or substituted hydrocarbon radical.
In above-mentioned technical proposal, R2、R3、R4Independent is preferably (CH2)aOH or (CH2)bCH3One of.
In above-mentioned technical proposal, preferably a=2~4, b=0~2.
In above-mentioned technical proposal, R5、R6Independent is preferably (CH2)cOr (CH2)c(CHOH)d(CH2)eOne of.
In above-mentioned technical proposal, preferably c=1 or 2, d=0 or 1, e=1 or 2.
In above-mentioned technical proposal, R8、R9Independent is preferably CH3、C2H5、(CH2)2OH or C6H5CH2One of.
In above-mentioned technical proposal, R10Preferably CH3、C2H5、(CH2)2OH or C6H5CH2One of；Or R8X-Preferably
CH2COO-、(CH2)3SO3 -、CH2(CHOH)CH2SO3 -One of.
In above-mentioned technical proposal, R11With R12The sum of preferably C7~C23Alkyl or substituted hydrocarbon radical.
In above-mentioned technical proposal, M is independently preferably hydrogen, alkali metal or by formula NR13(R14)(R15)(R16) shown in group
At least one.
In above-mentioned technical proposal, R13、R14、R15、R16Independent is preferably H, (CH2)aOH or (CH2)bCH3One of.
In above-mentioned technical proposal, Y1、Y2Preferably COO-Or SO3 -One of.
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, the solid filler be preferably inorganic oxysalt, metal halide, organic carboxyl acid and/
Or at least one of its salt, urea, biuret etc.；The further preferred inorganic oxysalt is preferably carbonate, carbonic acid
Hydrogen salt, sulfate, phosphate, borate；The organic carboxyl acid and/or its salt be preferably formates, acetate, tartaric acid and/
Or its salt, citric acid and/or its salt, phthalic acid and/or its salt, gallic acid and/or its salt；It is still more preferably described
Solid packing is preferably sodium carbonate, sodium bicarbonate, Boratex, sodium chloride, sodium acetate, tartaric acid, sodium tartrate, citric acid, lemon
At least one of lemon acid sodium, phthalic acid potassium, urea, biuret.
In above-mentioned technical proposal, the binder be preferably dextrin, epoxy resin, polyacrylamide, starch, cellulose,
At least one of polyethylene glycol etc.；The further preferably at least one of polyacrylamide, starch, polyethylene glycol.
In above-mentioned technical proposal, polyamine surfactant in the solid foam water discharge agent helps surface-active, solid filler
Mass ratio with binder is preferably 1: (0.1~10): (0.1~200): (0.01~0.1).
Resisting high temperature, high salt solid foam water discharge agent of the present invention, can be by the polyamine surfactant and cosurfactant
It is obtained by mixing with the solid packing and binder in required ratio, preferably with following for solving two skill of technical problem
Art scheme obtains.
To solve above-mentioned technical problem two, The technical solution adopted by the invention is as follows: a kind of above-mentioned solution technical problem
One of described in resisting high temperature, high salt solid foam water discharge agent preparation method, comprising the following steps:
(1) preparation of polyamine surfactant:
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, obtains acyl
Amine compounds R0CO(NHCH2CH2)mNH2；Wherein, R0Selected from C3~C31One of alkyl or substituted hydrocarbon radical, R ' are selected from H, C1~
C8One of alkyl, m=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 at high temperature under high pressure
Catalysis reaction generates corresponding amine, or uses: the R that step a is synthesized0CO(NHCH2CH2)mNH2With metal hydride H-Y+Non-
Reduction reaction is carried out in protic, obtains R0CH2(NHCH2CH2)mNH2；Wherein, Y+For metallic compound, metal alkyl
Close object, metal amide；
C, alkylated reaction:
Using one halogenated hydrocarbons-sodium-hydroxide method, aldehydic acid oxidizing process, or using the aldehyde catalytic hydrogenation method included the following steps:
The R that step b is synthesized0CH2(NHCH2CH2)mNH2, R " CHO and H2In short chain alcohol solvent, react to obtain using metallic catalyst
In general molecular formula shown in formula (1) the tertiary amine nonionic surfactant of s1=t1=s2=t2=0 to get arrive the polyamines surface
Activating agent；The short carbon chain alcohol is selected from C1~C5Alkyl or substituted hydrocarbon radical alcohol；R " is selected from H, C1~C5In alkyl or substituted hydrocarbon radical
It is a kind of；R0CH2(NHCH2CH2)mNH2: R " CHO:H2Molar ratio be 1: (3~20): (5~40)；
Or it is further obtained in general molecular formula shown in formula (1) in s1=t1 and s2=t2 at least within by step d reaction
One of be 1 amphoteric ionic surfactant:
D, quaternization reaction:
By step c obtain tertiary amine nonionic surfactant and the ionization reagent of s1=t1=s2=t2=0 with mole
Than 1:(1~5) in short carbon chain alcohol aqueous solution, reacted 1~10 hour production (1) in 50~120 DEG C of reaction temperature shown in
At least one in s1=t1 and s2=t2 be 1 zwitterionic surfactant to get arrive the polyamine surfactant；
The ionization reagent is selected from XR5Y1M or X R6Y2At least one of N, wherein M and N is independently selected from one in alkali metal
Kind, X is one of chlorine, bromine or iodine；The volume fraction of short carbon chain alcohol is 0~100% in short carbon chain alcohol aqueous solution；
(2) according to required mass fraction, the polyamine surfactant, cosurfactant, solid of step (1) synthesis are filled out
Material and binder are uniformly mixed, are then pressed into type, and the solid foam draining is made
In above-mentioned technical proposal, the shape of the solid foam water discharge agent 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 NaBH4One 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, metallic catalyst is preferably one of Rancy Ni or Pd/C in step c, further excellent
It is selected as Rancy Ni.
In above-mentioned technical proposal, short carbon chain alcohol is preferably at least one of ethyl alcohol, propyl alcohol or isopropanol in step c.
In above-mentioned technical proposal, R " is preferably H, CH in step c3Or CH2One of OH.
In above-mentioned technical proposal, R in step c0CH2(NHCH2CH2)mNH2: R " CHO:H2Molar ratio be preferably 1: (4~
10):: (5~20).
In above-mentioned technical proposal, the molar ratio of tertiary amine nonionic surfactant and ionization reagent is 1:(1 in step d
~1.5).
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 XR5Y1M or X R6Y2The example of N has but is 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..
Resisting high temperature, high salt solid foam water discharge agent of the present invention has good compatibility, can also contain commonly used in the art
Other inorganic agents.
In order to solve the above-mentioned technical problem three, the technical solution adopted by the present invention is as follows: in a kind of above-mentioned technical proposal
Application of any resisting high temperature, high salt solid foam water discharge agent in gas well water pumping gas production.
In above-mentioned technical proposal, the resisting high temperature, high salt solid foam water discharge agent is applied and is not particularly limited, this field skill
Art personnel can be applied according to existing drainage gas production technology, such as but not limit preferred acidic high temperature and high salt ultra-deep gas
Well, high temperature acid gas-containing gas reservoir, formation temperature are 150~200 DEG C, 500~200000mg/L of total salinity of formation brine,
H2S and CO2Content 0~35%.
What the present invention used contains the polyamine surfactant 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
Exactly this resisting high temperature, high salt solid foam water discharge agent and preparation method and its application in water pumping gas production.
The thermal decomposition temperature of polyamine surfactant 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；Secondly, more hydrophilic radicals in molecule, on the one hand increase salt resistance
Property, the amount increase of the combination water and irreducible water that carry foaming agent, foam carrier amount enhancing is analysed liquid and is slowed down；Point
Containing the hetero atom responded to pH in son, the acidic high-temperature ultradeep well water pumping gas production with high salt applied to 200 DEG C is made it possible to
Cheng Zhong.
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 1 in above-mentioned technical proposal) and
2) total content or total concentration.
Using technical solution of the present invention, according to SY/T 6465-2000 " foam drainage gas recovery foaming agent evaluation method "
Foaming properties test is carried out to the foaming water discharge agent, 0.02~0.12% foaming water discharge agent is in 0~200,000mg/L salinity
In salt water, when being free of kerosene, before and after high temperature ageing, foam height reaches 170mm, takes liquid rate up to 93.9%, 0.12% foam
Water discharge agent is in 100,000mg/L salinity salt water, and when containing 10~30wt% kerosene, foam height reaches 153mm, takes liquid rate and reaches
88.5%, there is excellent heat-resistant salt-resistant oil resistance in acidic environment, achieve preferable technical effect.
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 HFS01
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 drying pressure reactor equipped with agitating device17H33CH2
(NHCH2CH2)5NH2, 200 grams of isopropanols, after 6 grams of Rancy Ni and 109.2 grams of (3.6 moles) of formaldehyde mixing, H is passed through after deoxidation2
Reduction reaction is carried out in 110~140 DEG C of reactions, until continuing heat preservation 1 hour after inhaling hydrogen, post-processing obtains polyamine compounds1
(R1=C18H35, m=5, R2=R3=R4=CH3, t1=t2=s1=s2=0).
D, by polyamine compounds1(R1=C18H35, m=5, R2=R3=R4=CH3, t1=t2=s1=s2=0) hydroxyl
60 grams of propanesulfonate product, C16H33SO360 grams of Na, 150 grams of sodium sulphate, 50 grams of sodium tartrate, 70 grams of potassium chloride be uniformly mixed,
Rodlike, obtained foam drainage rod HFS01 is pressed into after adding 50 grams of 10% polyethylene glycol mixing.
(2) HFS01 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%.
Referring to SY/T 6465-2000 " foam drainage gas recovery foaming agent evaluation method " standard, HFS01 solution is measured
The performances such as foaming power, foam stability, fluid-carrying capability, the results are shown in Table 1.
It is tested using the acidproof aging equipment of pressure resistance, after 180 DEG C of agings for 24 hours, redeterminates foaming power, foam is stablized
The performances such as property, fluid-carrying capability, the results are shown in Table 1.
[embodiment 2]
With [embodiment 1], difference when measure HFS01 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:
D, polyamine compounds1(R1=C18H35, m=5, R2=R3=R4=CH3, t1=t2=s1=s2=0) and 58.2 grams
(0.1 mole) is mixed in 29.5 grams of (0.15 mole) 3- chlorine-2-hydroxyl propanesulfonates and 100 milliliters of ethanol/waters (v/v=1)
In four-hole boiling flask equipped with mechanical stirring, thermometer and reflux condensing tube, it is heated to back flow reaction 5 hours.Solvent is evaporated off, is added
Water obtains polyamine compounds1(R1=C18H35, m=5, R2=R3=R4=CH3, t1=t2=s1=s2=0) the third sulphur of hydroxyl
Sour sodium product.
E, by polyamine compounds1(R1=C18H35, m=5, R2=R3=R4=CH3, t1=t2=s1=s2=0) hydroxyl
50 grams of propanesulfonate product, C16H33OC2H4N+(CH3)3Br-40 grams, C16H33SO310 grams of K, 150 grams of sodium sulphate, sodium tartrate 50
Gram, 70 grams of potassium chloride be uniformly mixed, add 50 grams of 10% polyethylene glycol mixing after be pressed into it is rodlike, be made foam drainage rod HFS02.
[embodiment 4]
With [embodiment 1], difference when measure HFS02 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 4.
[embodiment 5]
(1) preparation of foam discharging agent HFS03:
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 drying pressure reactor equipped with agitating device15H31CH2
(NHCH2CH2)2NH2, 150 grams of ethyl alcohol, after 2 grams of Rancy Ni and 105.6 grams of (2.4 moles) of acetaldehyde mixing, H is passed through after deoxidation2?
110~140 DEG C of reactions carry out reduction reaction, until continuing heat preservation 1 hour after inhaling hydrogen, post-processing obtains polyamine compounds2(R1
=C16H33, m=2, R2=R3=R4=C2H5, t1=t2=s1=s2=0).
D, by polyamine compounds2(R1=C16H33, m=2, R2=R3=R4=C2H5, t1=t2=s1=s2=0) 15 grams,
C22H45OC2H4N+(CH2CH2OH)2(CH3)CH2COO-90 grams, internal olefin sulphonates IOS (C19~23) 30 grams, phthalic acid potassium 30
Gram, 30 grams of Boratex, 100 grams of biuret, add 30 grams of 5% polyglycol solution mixing after be pressed into it is rodlike, be made foaming water discharge
Stick HFS03.
(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], difference when measure HFS03 performance, with hydrochloric acid by pH be adjusted to 7,4 and 2 simulation neutrality and
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 HFS04:
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 (0.4 mole) is added into the drying pressure reactor equipped with agitating device
C21H43CH2NHCH2CH2NH2, 200 grams of isopropanols, after 3.5 grams of Rancy Ni and 144.0 grams of (2.4 moles) of hydroxyl acetaldehyde mixing, go
H is passed through after oxygen2Reduction reaction is carried out in 110~140 DEG C of reactions, until continuing heat preservation 1.5 hours after inhaling hydrogen, post-processing is obtained
Polyamine compounds3(R1=C22H45, m=1, R2=R3=R4=C2H4OH, t1=t2=s1=s2=0).
D, polyamine compounds3(R1=C22H45, m=1, R2=R3=R4=C2H4OH, t1=t2=s1=s2=0) 50 grams
(0.1 mole) and 15.9 grams of (0.12 mole) potassium chloroacetates and 100 milliliters of isopropanol/waters (v/v=0.2) are mixed in equipped with machinery
In the four-hole boiling flask of stirring, thermometer and reflux condensing tube, it is heated to back flow reaction 7 hours.Solvent is evaporated off, water is added, obtains
Polyamine compounds3(R1=C22H45, m=1, R2=R3=R4=C2H4OH, t1=t2=s1=s2=0) potassium acetate product.
E, by polyamine compounds3(R1=C22H45, m=1, R2=R3=R4=C2H4OH, t1=t2=s1=s2=0)
Potassium acetate product 90g, C16H33OC2H4N+(CH3)2CH2COO-20 grams, 50 grams of potassium citrate, 200 grams of urea, 20 grams of potassium carbonate, second
20 grams of sour sodium are uniformly mixed, and are pressed into rodlike, obtained foam drainage rod after adding 30 grams of 1% polyacrylamide solution mixing
HFS04。
(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], difference when measure HFS04 performance, with hydrochloric acid by pH be adjusted to 7,4 and 2 simulation neutrality and
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 HFS05:
A, 56.7 grams are added in the reaction flask of Xiang Peiyou mechanical stirring, thermometer, dropping funel and atmospheric distillation plant
(0.55 mole) diethylenetriamine and 13.8 grams of (0.1 mole) potash solids, 158.3 grams are slowly instilled under stirring, and (0.5 rubs
You) methyl abietate (formula 2), reacts 8 hours in 120~160 DEG C of reaction temperature, is collected simultaneously the methanol that reaction generates
Obtain required amide compound C19H29CO(NHCH2CH2)2NH2, yield 86.9%.
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
38.7 grams of (0.1 mole) C19H29CO(NHCH2CH2)2NH240wt% dioxane solution, drip and be slowly warming up to 30 DEG C of left sides
Right reaction 6 hours.Reaction solution is carefully poured into ice water, it is post-treated to obtain rosin polyamine compounds C19H29CH2
(NHCH2CH2)2NH2, yield 75.8%.
C, 149.2 grams of (0.4 mole) C are added into the drying pressure reactor equipped with agitating device19H29CH2
(NHCH2CH2)2NH2, 200 grams of propyl alcohol, after 7 grams of Rancy Ni and 72.0 grams of (2.4 moles) of formaldehyde mixing, H is passed through after deoxidation2?
120~140 DEG C of reactions carry out reduction reaction, until continuing heat preservation 1 hour after inhaling hydrogen, post-processing obtains polyamine compounds4(R1
=C20H31, m=2, R2=R3=R4=CH3, t1=t2=s1=s2=0).
D, by polyamine compounds4(R1=C20H31, m=2, R2=R3=R4=CH3, t1=t2=s1=s2=0) and 100
Gram, C22H45O(C2H4O)2C2H4N+(CH3)2CH2COO-10 grams, a- alkene sulfonate AOS (C14~18) 5 grams, phthalic acid potassium 30
Gram, 50 grams of Boratex, 100 grams of biuret, add 30 grams of 5% polyglycol solution mixing after be pressed into it is rodlike, be made foaming water discharge
Stick HFS05.
(2) it with [embodiment 1], the results are shown in Table shown in 9.
[embodiment 10]
With [embodiment 9], difference when measure HFS05 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 10.
[embodiment 11]
With [embodiment 1], the difference is that when measurement HFS01~HFS05 performance, difference addition 10wt%,
The kerosene of 30wt%, simulation water are 100,000mg/LNaCl, be the results are shown in Table shown in 11.
[comparative example 1]
With [embodiment 1], the difference is that respectively with polyamine compounds1(R1=C18H35, m=5, R2=R3=R4=
CH3, t1=t2=s1=s2=0) and 100 grams, C16H33SO3100 grams of substitution " polyamine compounds of K1(R1=C18H35, m=5, R2=
R3=R4=CH3, t1=t2=s1=s2=0) and 50 grams, C16H33SO350 grams of Na ", other additives are constant, form foaming water discharge
Stick HFS06 and HFS07, simulation water are 100,000mg/LNaCl, be the results are shown in Table shown in 12.
[comparative example 2]
With [embodiment 3], the difference is that respectively with polyamine compounds1(R1=C18H35, m=5, R2=R3=R4=
CH3, t1=t2=s1=s2=0) 100 grams of hydroxypropionate sodium product, C16H33OC2H4N+(CH3)3Br-100 grams of substitutions are " more
Amine compounds1(R1=C18H35, m=5, R2=R3=R4=CH3, t1=t2=s1=s2=0) hydroxypropionate sodium product 50
Gram, C16H33OC2H4N+(CH3)3Br-40 grams, C16H33SO310 grams of K ", other additives are constant, form foam drainage rod HFS08
And HFS09, simulation water are 100,000mg/LNaCl, be the results are shown in Table shown in 12.[comparative example 3]
With [embodiment 5], the difference is that respectively with polyamine compounds2(R1=C16H33, m=2, R2=R3=R4=
C2H5, t1=t2=s1=s2=0) and 135 grams, C22H45OC2H4N+(CH2CH2OH)2(CH3)CH2COO-135 grams, inner olefin sulfonic acid
Salt IOS (C19~23) 135 grams of substitution " polyamine compounds2(R1=C16H33, m=2, R2=R3=R4=C2H5, t1=t2=s1=s2
=0) 15 grams, C22H45OC2H4N+(CH2CH2OH)2(CH3)CH2COO-90 grams, internal olefin sulphonates IOS (C19~23) 30 grams ", other
Additive is constant, forms foam drainage rod HFS10, HFS11 and HFS12, and simulation water is 100,000mg/LNaCl, the results are shown in Table
Shown in 12.
[comparative example 4]
With [embodiment 7], the difference is that respectively with polyamine compounds3(R1=C22H45, m=1, R2=R3=R4=
C2H4OH, t1=t2=s1=s2=0) 110 grams of potassium acetate product, C16H33OC2H4N+(CH3)2CH2COO-110 grams of substitutions are " more
Amine compounds3(R1=C22H45, m=1, R2=R3=R4=C2H4OH, t1=t2=s1=s2=0) 90 grams of potassium acetate product,
C16H33OC2H4N+(CH3)2CH2COO-20 grams ", other additives are constant, form foam drainage rod HFS13 and HFS14, simulate water
It is 100,000mg/LNaCl, the results are shown in Table shown in 12.
[comparative example 5]
With [embodiment 9], the difference is that respectively with C22H45O(C2H4O)2C2H4N+(CH3)2CH2COO-115 grams, polyamines
Compound4(R1=C20H31, m=2, R2=R3=R4=CH3, t1=t2=s1=s2=0) and 115 grams, a- alkene sulfonate AOS
(C14~18) 115 grams of substitution " polyamine compounds4(R1=C20H31, m=2, R2=R3=R4=CH3, t1=t2=s1=s2=0)
100 grams, C22H45O(C2H4O)2C2H4N+(CH3)2CH2COO-10 grams, a- alkene sulfonate AOS (C14~18) 5 grams ", other additives
It is constant, foam drainage rod HFS15, HFS16 and HFS17 are formed, simulation water is 100,000mg/LNaCl, be the results are shown in Table shown in 12.
[comparative example 6]
With [embodiment 1], the difference is that with " C17H33CO(NHCH2CH2)5NH250 grams, C16H33SO350 grams of Na "
Substitute " polyamine compounds1(R1=C18H35, m=5, R2=R3=R4=CH3, t1=t2=s1=s2=0) 50 grams,
C16H33SO350 grams of Na ", other additives are constant, form foam drainage rod HFS18, and simulation water is 100,000mg/LNaCl, knot
Fruit is shown in Table 12.
[comparative example 7]
With [comparative example 1], the difference is that pH is adjusted to 7 and 4 simulation neutrality and sour gas with hydrochloric acid when measurement performance
Body environment, the results are shown in Table shown in 13.
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
Claims (10)
1. solid foam water discharge agent, in terms of mass fraction, including following components:
1) 1 part of polyamine surfactant；
2) 0.01~100 portion of cosurfactant；
3) 0.05~1000 part of solid filler；
4) 0~0.5 part of binder；
Wherein, the polyamine surfactant is selected from least one of 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 C1~C5Alkyl or substitution
Alkyl, R5、R6It is independently selected from (CH2)cOr (CH2)c(CHOH)d(CH2)eOne of, any integer in c=1~4, d=0~
Any integer in 3, any integer in e=1~4；Y1、Y2It is independently selected from COO-、SO3 -、OSO3 -One of；M is ethylene
Amido segment number, any integer in m=1~10；T1, t2 are positive changes, and s1, s2 are respectively R5Y1、R6Y2Substituent group
Number, t1=s1=0 or 1, t2=s2=0 or 1.
2. solid foam water discharge agent according to claim 1, it is characterised in that the cosurfactant be selected from both sexes from
At least one of son or cationic surfactant, anionic surfactant；The amphoteric ion or cationic surface are living
Property agent have formula (2) shown in general molecular formula:
In formula (2), R7For selected from C4~C32One of alkyl or substituted hydrocarbon radical, R8、R9It is independently selected from (CH2)aOH、(CH2)bCH3
Or C6H5CH2One of, R10Selected 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), R11With R12The sum of for selected from C3~C31One of alkyl or substituted hydrocarbon radical, M be selected from hydrogen, alkali metal or by
Formula NR13(R14)(R15)(R16) shown at least one of group, R13、R14、R15、R16To be independently selected from H, (CH2)aOH or
(CH2)bCH3One of, any integer in a=2~4, b=0~5.
3. solid foam water discharge agent according to claims 1 and 2, it is characterised in that the R1、R7It is independently selected from C8~C24Hydrocarbon
Base or substituted hydrocarbon radical；R11With R12The sum of be C7~C23Alkyl or substituted hydrocarbon radical；R2、R3、R4It is independently selected from (CH2)aOH or (CH2)bCH3One of, any integer in a=2~4, any integer in b=0~5；R5、R6It is independently selected from (CH2)cOr (CH2)c
(CHOH)d(CH2)eOne of, any integer in c=1~2, any integer in d=0~1, any in e=1~2
Integer；R8、R9It is independently selected from CH3、C2H5、(CH2)2OH or C6H5CH2One of；R10For CH3、C2H5、(CH2)2OH、C6H5CH2
One of or R10X-For CH2COO-、(CH2)3SO3 -、CH2(CHOH)CH2SO3 -One of；Y1、Y2It is independently selected from COO-、SO3 -
One of；M=1~5, n=0~5, p=0~5.
4. solid foam water discharge agent according to claim 1, it is characterised in that the solid filler be inorganic oxysalt,
At least one of metal halide, organic carboxyl acid and/or its salt, urea, biuret etc.；The binder is dextrin, epoxy
At least one of resin, polyacrylamide, starch, cellulose, polyethylene glycol；The further preferred inorganic oxysalt is excellent
It is selected as carbonate, bicarbonate, sulfate, phosphate, borate；The organic carboxyl acid and/or its salt are preferably formates, second
Hydrochlorate, tartaric acid and/or its salt, citric acid and/or its salt, phthalic acid and/or its salt, gallic acid and/or its salt；More
The further preferred solid packing is preferably sodium carbonate, sodium bicarbonate, Boratex, sodium chloride, sodium acetate, tartaric acid, winestone
At least one of sour sodium, citric acid, sodium citrate, phthalic acid potassium, urea, biuret；The binder is preferably poly-
At least one of acrylamide, starch, polyethylene glycol.
5. solid foam water discharge agent according to claim 1, it is characterised in that the polyamine surfactant helps surface-active
The mass ratio of agent, solid filler and binder is 1: (0.1~10): (0.1~200): (0.01~0.1).
6. the preparation method of any solid foam water discharge agent of Claims 1 to 5, comprising the following steps:
(1) preparation of polyamine surfactant:
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, obtains amidation
Close object R0CO(NHCH2CH2)mNH2；Wherein, R0Selected from C3~C31One of alkyl or substituted hydrocarbon radical, R ' are selected from H, C1~C8's
One of alkyl, m=1~10, catalyst in alkali metal hydroxide, alkali metal alcoholates, alkali carbonate extremely
Few one kind；
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, alkylated reaction:
Using one halogenated hydrocarbons-sodium-hydroxide method, aldehydic acid oxidizing process, or using the aldehyde catalytic hydrogenation method included the following steps: will walk
The R of rapid b synthesis0CH2(NHCH2CH2)mNH2, R " CHO and H2In short chain alcohol solvent, react to obtain formula using metallic catalyst
(1) the tertiary amine nonionic surfactant of s1=t1=s2=t2=0 is in general molecular formula shown in get living to the polyamines surface
Property agent；The short carbon chain alcohol is selected from C1~C5Alkyl or substituted hydrocarbon radical alcohol；R " is selected from H, C1~C5One in alkyl or substituted hydrocarbon radical
Kind；R0CH2(NHCH2CH2)mNH2: R " CHO:H2Molar ratio be 1: (3~20): (5~40)；
Or at least one in s1=t1 and s2=t2 in general molecular formula shown in formula (1) is further obtained by step d reaction
Amphoteric ionic surfactant for 1:
D, quaternization reaction:
By the step c tertiary amine nonionic surfactant for obtaining s1=t1=s2=t2=0 and ionization reagent with molar ratio 1:
(1~5) reacts s1=shown in 1~10 hour production (1) in 50~120 DEG C of reaction temperature in short carbon chain alcohol aqueous solution
At least one in t1 and s2=t2 be 1 zwitterionic surfactant to get arrive the polyamine surfactant；It is described
Ionization reagent be selected from XR5Y1M or X R6 Y2At least one of N, wherein M and N is independently selected from one of alkali metal, X
For one of chlorine, bromine or iodine；The volume fraction of short carbon chain alcohol is 0~100% in short carbon chain alcohol aqueous solution；
(2) according to required mass fraction, by the polyamine surfactant 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 is made.
7. the preparation method of solid foam water discharge agent according to claim 6, it is characterised in that R described in step a0COOR’、H
(NHCH2CH2)mNH2, catalyst molar ratio 1:(1~1.3): (0~0.1), catalyst be sodium hydroxide, potassium hydroxide, carbon
At least one of sour sodium, potassium carbonate.
8. the preparation method of solid foam water discharge agent according to claim 6, it is characterised in that H described in step b-Y+For
LiAlH4、LiAlH(OEt)3Or NaBH4One of, aprotic solvents be ether, tetrahydrofuran, in dioxane at least
It is a kind of.
9. the preparation method of solid foam water discharge agent according to claim 6, it is characterized in that metallic catalyst described in step c
Selected from one of Rancy Ni, Pd/C；Short carbon chain alcohol is selected from least one of methanol, ethyl alcohol, propyl alcohol or isopropanol；R " choosing
From H, CH3Or CH2One of OH；R0CH2(NHCH2CH2)mNH2: R " CHO:H2Molar ratio be 1: (4~10): (5~20)；
Tertiary amine nonionic surfactant described in the step d: the molar ratio of ionization reagent is 1: (1~1.5)；Short carbon chain alcohol
Selected from least one of methanol, ethyl alcohol, propyl alcohol or isopropanol.
10. application of any solid foam water discharge agent of Claims 1 to 5 in gas well water pumping gas production.
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| CN104140802A (en) * | 2013-10-29 | 2014-11-12 | 中国石油化工股份有限公司 | Foam drainage agent for gas well drainage gas recovery |
| CN104974730A (en) * | 2015-06-12 | 2015-10-14 | 中国石油天然气股份有限公司 | High temperature-resistant high-mineralization degree foam scrubbing agent and its preparation method and use |
| CN106986796A (en) * | 2017-05-24 | 2017-07-28 | 陕西科技大学 | A kind of Gemini surface active agent and its preparation method and application |
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| CN104140802A (en) * | 2013-10-29 | 2014-11-12 | 中国石油化工股份有限公司 | Foam drainage agent for gas well drainage gas recovery |
| CN104974730A (en) * | 2015-06-12 | 2015-10-14 | 中国石油天然气股份有限公司 | High temperature-resistant high-mineralization degree foam scrubbing agent and its preparation method and use |
| CN106986796A (en) * | 2017-05-24 | 2017-07-28 | 陕西科技大学 | A kind of Gemini surface active agent and its preparation method and application |
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