CN109554171A - Environment-friendlysticky sticky soil stabilizer - Google Patents
Environment-friendlysticky sticky soil stabilizer 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
- C09K8/02—Well-drilling compositions
- C09K8/03—Specific additives for general use in well-drilling compositions
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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
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/607—Compositions for stimulating production by acting on the underground formation specially adapted for clay formations
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/12—Swell inhibition, i.e. using additives to drilling or well treatment fluids for inhibiting clay or shale swelling or disintegrating
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Abstract
The invention discloses a kind of environment-friendlysticky sticky soil stabilizers, including 5~30 portions of benzyl quaternary ammonium salt, 10~30 parts of heterocycle polyquaterniums in parts by weight, 35~40 parts of sulphonyl quaternary ammonium salts and 5~40 parts of choline chlorides；Wherein, benzyl quaternary ammonium salt is reacted by N- amino ethyl ethanolamine, formaldehyde and benzyl chloride and is made；Heterocycle polyquaternium is reacted by N- amino ethyl ethanolamine, formaldehyde and dichloroether to be made；Sulphonyl quaternary ammonium salt is made by diethanol amine, formaldehyde, dithyl sulfate and bis- (diethanol amine) methane reactions；The clay stabilizer has both wide pH application environment, high temperature tolerance and height and prevents swollen performance, it is suitable for the various underground work liquid that pH value is between 1~14, resistance to 150 DEG C of high temperature, anti-dilative > 88%, prevent that the swollen performance duration is verified more than 1 month, while by biocompatibility experiment, half lethal concentration LC50 > 10000mg/L, with the excellent feature of environmental protection, it is suitable for use as the additive of all kinds of underground work liquid such as preparing fracturing fluid, acid solution, perforating fluid and workover fluid.
Description
Technical field
The present invention relates to oilfield prospecting developing underground work technical field, in particular to a kind of environment-friendlysticky sticky soil stabilization
Agent.
Background technique
Clay mineral mainly has montmorillonite, kaolinite, illite, chlorite, illite/smectite mixed layer, green deceives people several major class such as layer.
Clay mineral widely exists in oil and gas reservoir.These clay mineral grains during the exploration and development in oil field such as drilling well,
Complete well, acidification, pressure break, encounter external water-based fluid in the injecting process after its own will generate expansion or migration, thus meeting
It results in blockage to hole or fracture medium, influences penetrating power and oil gas well production.Generally for the permeability for protecting oil-gas Layer,
It is swollen for the clay of mud shale or loam mould stratum during fracture acidizing transformation or workover treatment to improve oil and gas production
The problems such as swollen, alleviates its expansion or migration using the clay stabilizer of inhibition.
So far from the fifties, domestic and foreign scholars are by the research and extension application to clay stabilizer, it is excellent have selected it is tens of
Kind clay stabilizer.These clay stabilizers can be divided into following a few major class according to chemical composition:
I, salt, including inorganic salts and organic salt；It mainly has sodium chloride, potassium chloride, ammonium chloride, guanidine hydrochloride, guanidine acetate
Deng.Salt clay stabilizer be by increasing its concentration, thus reduce surface of clay diffusion electric double layer thickness and zeta current potential and
It works；The characteristics of this kind of stabilizer be it is cheap, short-term preventive effect of expansion is good.Disadvantage be to prevent that swollen validity period is short, and it is right
Inhibit fine migration effect poor.
II, cationic surface active agent mainly include quaternary ammonium salt cationic surfactant, pyridine salt type surfactant
And imidazoline salt form surfactant etc..The cation of this kind of surfactant has surface-active, enables it to be adsorbed on clay
Electronegative surface, neutralize the elecrtonegativity of clay and prevent clay swell, while can also be by hydrogen bond and electrostatic attraction by particle
The migration of particle is linked up and inhibited with surface of stratum.Although it has many advantages, such as strong adsorption force, can water resistant rinse, this
The use of class clay stabilizer can make surface of stratum be transformed into lipophilicity, reduce the permeability of oil gas phase.
III, alkyl halogen silyl class, mainly there is dimethyldichlorosilane, diphenyldichlorosilane, ethyl trichlorine
Monosilane etc..Alkyl halogen silyl class clay stabilizer can be reacted with the hydroxyl of surface of clay, become the water-wetted surface of clay
At oil-wetted surface, inhibit clay swell, it can also generate condensation polymer by hydrolysis, polycondensation, with hydrogen bond by small bits of clay and ground
Layer surface is bridged and fixes particle；However alkyl halogen silyl class clay stabilizer has the surface with cationic
The same disadvantage of activating agent.
IV, inorganic polymeric species, mainly there is hydroxy Al, iron carbonyl, basic zirconium chloride etc..These inorganic cation type polymer
Polynuclear hydroxy bridge complex ion can be dissociateed in water.Since polynuclear hydroxy bridge complex ion has very high positive electricity price and structure and clay-phase
Seemingly, so energy adsorbed close reduces its elecrtonegativity, to effectively inhibit clay swell on the electronegative surface of clay；This
Outside, polynuclear hydroxy bridge complex ion the electronegative small bits of clay in surface and electronegative surface of stratum can be bridged and by particle
It is fixed, prevent fine migration.However, although it, which has, prevents that swollen validity period has compared with what salt and cationic surface active agent were all grown
Point, but it is not suitable for carbonate strata, and is only capable of using under mild acid conditions.
V, organic cation type polymer.Organic cation type polymer can dissolve in water, dissociate generation polycation,
These polycations both can neutralize the elecrtonegativity of surface of clay, and can bridge them in clay crystalline substance Inter layer adsorption by absorption
Get up, inhibits clay swell, and small bits of clay can be bridged and effectively inhibit fine migration in surface of stratum.This kind of stabilization
The advantages that agent is with that can act on different types of stratum, and acidproof, oil resistant, water wash away, and dosage is few, quick, and validity period is long,
It therefore is also a kind of clay stabilizer being most widely used.By its cation it is different can be divided into again polyquaternary amine salt,
Poly- quaternary phosphonium salt and poly- tertiary sulfosalt three classes.Wherein, polyquaternary amine salt is important research object both at home and abroad in recent years, and at present
Most promising first stability agent.
In conclusion above-mentioned conventional clay stabilizer has the disadvantage that the addition of the temporary steady agent KCl of (1) clay results in
The system contains the chloride ion of higher concentration, and the chloride ion of high concentration can generate in conjunction with the organic matter in environment has three to cause effect
The chlorinated compound for answering (mutagenic effect, teratogenic effect, carcinogenic effect), seriously affects ecological environment；(2) existing clay is long
The steady for example poly- ammonium salt of agent or quaternary ammonium salt bio-toxicity with higher.As it can be seen that the introducing of the clay stabilizer of non-environmental protection type system must
Environmental protection pressure so is brought, is returned after being discharged to ground, it is necessary to carry out corresponding harmless treatment, and then also improve oil-gas field development
Cost.Therefore, it is necessary to develop a kind of clay stabilizer with strong rejection capability and the excellent feature of environmental protection, the row of returning is reduced to realize
The processing cost of liquid, and reduce the purpose of its pollution to water flooding.
Summary of the invention
The object of the present invention is to provide one kind have both wide pH application environment, temperature tolerance, it is excellent prevent swollen property and it is long-acting prevent it is swollen
The environment-friendlysticky sticky soil stabilizer of time.
For this purpose, technical solution of the present invention is as follows:
A kind of environment-friendlysticky sticky soil stabilizer, it is poly- including 5~30 portions of benzyl quaternary ammonium salt, 10~30 parts of heterocycles in parts by weight
Quaternary ammonium salt, 35~40 parts of sulphonyl quaternary ammonium salts and 5~40 parts of choline chlorides；Wherein, benzyl quaternary ammonium salt by N- amino ethyl ethanolamine,
Formaldehyde and benzyl chloride reaction are made；Heterocycle polyquaternium is reacted by N- amino ethyl ethanolamine, formaldehyde and dichloroether to be made；Sulphur
Acyl quaternary ammonium salt is made by diethanol amine, formaldehyde, dithyl sulfate and bis- (diethanol amine) methane reactions.
The chemical structural formula for participating in each reaction monomers of above-mentioned reaction is as follows:
N- amino ethyl ethanolamine:Formaldehyde: CH2=O, benzyl chloride:
Dichloroether:Diethanol amine:
Dithyl sulfate:Bis- (diethanol amine) methane:
Wherein, in the preparation process of benzyl quaternary ammonium salt, heterocycle polyquaternium and sulphonyl quaternary ammonium salt, due to commercially available formaldehyde
Reagent is the formalin that content of formaldehyde is 37~40wt.%, therefore during the preparation process, formaldehyde is with formalin
Form participates in reaction, and corresponding additional amount is converted to obtain with formaldehyde mass fraction.
It is preferred that the benzyl quaternary ammonium salt is by the N- amino ethyl ethanolamines of 100~140 parts by weight, 65~75 parts by weight
Formaldehyde and the reaction of the benzyl chloride of 140~150 parts by weight are made.
It is preferred that the benzyl quaternary ammonium salt the preparation method comprises the following steps: being added N- amino ethyl ethanolamine to 2~2.5 times of N-
In the water of amino ethyl ethanolamine and stir to being completely dissolved；Under stirring condition, 30~45 DEG C are warming up to, formalin is added dropwise
Solution is warming up to 80~90 DEG C, then benzyl chloride is added dropwise after being added dropwise, being kept for 80~90 DEG C after being added dropwise, the reaction was continued
3~4h.
It is preferred that the heterocycle polyquaternium includes the N- amino ethyl ethanolamine of 110~130 parts by weight, 65~75 weight
The formaldehyde of part and the dichloroether of 80~90 parts by weight.
It is preferred that the heterocycle polyquaternium the preparation method comprises the following steps: being added N- amino ethyl ethanolamine to 2~3 times of N-
In the water of amino ethyl ethanolamine and stir to being completely dissolved；Under stirring condition, 40~55 DEG C are warming up to, formalin is added dropwise
Solution is warming up to 80~90 DEG C, then dichloroether is added dropwise after being added dropwise, 90~110 DEG C are warming up to after being added dropwise, after
16~20h of continuous reaction.
It is further preferred that in the preparation process of above-mentioned heterocycle polyquaternium, the rate of addition of the formalin is 6~
6.5g/min；The rate of addition of the dichloroether is 8~9g/min.
It is preferred that the sulphonyl quaternary ammonium salt includes the diethanol amine of 165~175 parts by weight, 20~30 parts by weight of formaldehyde, 240
Bis- (diethanol amine) methane of~260 parts sulfuric acid diethylesters and 25~35 parts by weight.
It is preferred that the sulphonyl quaternary ammonium salt the preparation method comprises the following steps: being added diethanol amine to 1~1.5 times of diethanol amine
In water and stir to being completely dissolved；Under stirring condition, 40~55 DEG C are warming up to, formalin is added dropwise, after being added dropwise
60~90 DEG C are warming up to, then dithyl sulfate is added dropwise, 100 DEG C are warming up to after being added dropwise, adds bis- (diethanol amine)
Methane, the reaction was continued 10~12h.
It is further preferred that the rate of addition of the formalin is 2~3g/ in the preparation process of above-mentioned sulphonyl quaternary ammonium salt
min；The rate of addition of the dithyl sulfate is 1~1.5g/min.
The environment-friendlysticky sticky soil stabilizer preparation method is simple, weighs benzyl quaternary ammonium salt, heterocycle polyquaternium, sulphonyl in proportion
Quaternary ammonium salt and choline chloride and being mixed evenly can be obtained, and it is each to be applied to fracturing fluid, acid solution, perforating fluid and workover fluid etc.
Dosage in class underground work liquid is 1~2wt.%.
Compared with prior art, which is to have both wide pH application environment, high temperature tolerance and height to prevent swollen performance
Environment-friendlysticky sticky soil stabilizer, is the various underground work liquid between 1~14 it is suitable for pH value, and heatproof is up to 150 DEG C, prevents swollen
Rate > 88% prevents that the swollen performance duration is verified more than 1 month, while by biocompatibility experiment, half lethal concentration LC50>
10000mg/L has the excellent feature of environmental protection, is suitable for use as all kinds of underground works such as preparing fracturing fluid, acid solution, perforating fluid and workover fluid
Make the additive of liquid.
Specific embodiment
The present invention is described further combined with specific embodiments below, but following embodiments absolutely not to the present invention have appoint
What is limited.
Embodiment 1
A kind of environment-friendlysticky sticky soil stabilizer, specific preparation process is as follows:
S1,100g N- amino ethyl ethanolamine is dissolved in 240mL water；Under stirring condition, be warming up to 30 DEG C, dropwise plus
Enter 170g, 37wt.% formalin, 80 DEG C are warming up to after being added dropwise, then 140g benzyl chloride is added dropwise, after being added dropwise
80 DEG C of the reaction was continued 3h are kept, benzyl quaternary ammonium salt is obtained；
S2,110g N- amino ethyl ethanolamine is dissolved in 300mL water；Under stirring condition, be warming up to 40 DEG C, dropwise plus
Enter 180g, 37wt.% formalin, last 30min, 80 DEG C are warming up to after being added dropwise, then bis- chloroethene of 80g is added dropwise
Ether lasts 10min, and 90 DEG C are warming up to after being added dropwise, the reaction was continued 16h, obtains heterocycle polyquaternium；
S3,165g diethanol amine is dissolved in 210mL water；Under stirring condition, be warming up to 40 DEG C, be added dropwise 60g,
37wt.% formalin, lasts 25min, and 60 DEG C are warming up to after being added dropwise, then 240g dithyl sulfate is added dropwise, and goes through
When 3h, 100 DEG C are warming up to after being added dropwise, bis- (diethanol amine) methane of 25g are added, and the reaction was continued 10h, obtains sulphonyl season
Ammonium salt；
S4, benzyl quaternary ammonium salt obtained in 5g above-mentioned steps S1, heterocycle polyquaternary amine obtained in 30g above-mentioned steps S2 are weighed
Salt, the commercially available choline chloride of sulphonyl quaternary ammonium salt and 25g obtained in 40g above-mentioned steps S3, is mixed evenly, obtains environmental protection
Type clay stabilizer.
Embodiment 2
S1,140g N- amino ethyl ethanolamine is dissolved in 280mL water；Under stirring condition, temperature 45 C is kept, dropwise
190g, 37wt.% formalin is added, 90 DEG C is warming up to after being added dropwise, then 150g benzyl chloride is added dropwise, is added dropwise
90 DEG C of the reaction was continued 4h are kept afterwards, obtain benzyl quaternary ammonium salt；
S2,130g N- amino ethyl ethanolamine and 320mL water are mixed, under stirring condition, is kept for 55 DEG C of temperature.Dropwise
190g37wt.% formalin is added, 30min is warming up to 90 DEG C after being added dropwise, then 90g dichloroether is added dropwise,
10min is lasted, 110 DEG C are warming up to after being added dropwise, the reaction was continued 20h obtains heterocycle polyquaternium；
S3,175g diethanol amine is dissolved in 230mL water；Under stirring condition, be warming up to 55 DEG C, be added dropwise 70g,
37wt.% formalin, lasts 25min, and 90 DEG C are warming up to after being added dropwise, then 260g dithyl sulfate is added dropwise, and goes through
When 3h, 100 DEG C are warming up to after being added dropwise, bis- (diethanol amine) methane of 35g are added, and the reaction was continued 12h, obtains sulphonyl season
Ammonium salt；
S4, benzyl quaternary ammonium salt obtained in 10g above-mentioned steps S1, heterocycle poly- season obtained in 30g above-mentioned steps S2 are weighed
Ammonium salt, the commercially available choline chloride of sulphonyl quaternary ammonium salt and 20g obtained in 40g above-mentioned steps S3, is mixed evenly, obtains ring
Guarantor's type clay stabilizer.
Embodiment 3
S1,120g N- amino ethyl ethanolamine is dissolved in 260mL water；Under stirring condition, be warming up to 40 DEG C, dropwise plus
Enter 180g, 37wt.% formalin, 85 DEG C are warming up to after being added dropwise, then 145g benzyl chloride is added dropwise, after being added dropwise
85 DEG C of the reaction was continued 3.5h are kept, benzyl quaternary ammonium salt is obtained；
S2, will be in 120g N- amino ethyl ethanolamine and 310mL water；Under stirring condition, 50 DEG C are warming up to, is added dropwise
185g37wt.% formalin, lasts 30min, and 85 DEG C are warming up to after being added dropwise, then 85g dichloroether is added dropwise, and goes through
When 10min, 100 DEG C are warming up to after being added dropwise, the reaction was continued 18h obtains heterocycle polyquaternium；
S3,170g diethanol amine is dissolved in 220mL water；Under stirring condition, be warming up to 50 DEG C, be added dropwise 65g,
37wt.% formalin, lasts 25min, and 75 DEG C are warming up to after being added dropwise, then 250g dithyl sulfate is added dropwise, and goes through
When 3h, 100 DEG C are warming up to after being added dropwise, bis- (diethanol amine) methane of 30g are added, and the reaction was continued 11h, obtains sulphonyl season
Ammonium salt；
S4, benzyl quaternary ammonium salt obtained in 30g above-mentioned steps S1, heterocycle poly- season obtained in 30g above-mentioned steps S2 are weighed
Ammonium salt, the commercially available choline chloride of sulphonyl quaternary ammonium salt and 5g obtained in 35g above-mentioned steps S3, is mixed evenly, obtains ring
Guarantor's type clay stabilizer.
Embodiment 4
S1,120g N- amino ethyl ethanolamine is dissolved in 266mL water；Under stirring condition, be warming up to 32 DEG C, dropwise plus
The formalin for entering 181g, 37wt.% is warming up to 82 DEG C after being added dropwise, then 144.7g benzyl chloride is added dropwise, and continues anti-
3h is answered, benzyl quaternary ammonium salt is obtained；
S2,120g N- amino ethyl ethanolamine is dissolved in 308mL water；Under stirring condition, be warming up to 50 DEG C, dropwise plus
The formalin for entering 187g, 37wt.%, lasts 30min, and 83 DEG C are warming up to after being added dropwise, then bis- chloroethene of 82g is added dropwise
Ether lasts 10min, and 90 DEG C are warming up to after being added dropwise, the reaction was continued 18h, obtains heterocycle polyquaternium；
S3,169g diethanol amine is dissolved in 221mL water；Under stirring condition, be warming up to 45 DEG C, be added dropwise 65g,
The formalin of 37wt.%, lasts 25min, and 80 DEG C are warming up to after being added dropwise, then 250g dithyl sulfate is added dropwise,
3h is lasted, is warming up to 100 DEG C, bis- (diethanol amine) methane of 30g are added, and the reaction was continued 10h, obtains sulphonyl quaternary ammonium salt；
S4, benzyl quaternary ammonium salt obtained in 10g above-mentioned steps S1, heterocycle poly- season obtained in 10g above-mentioned steps S2 are weighed
Ammonium salt, the commercially available choline chloride of sulphonyl quaternary ammonium salt and 40g obtained in 40g above-mentioned steps S3, is mixed evenly, obtains ring
Guarantor's type clay stabilizer.
Performance test:
Hereinafter the environment-friendlysticky sticky soil stabilizer of Examples 1 to 4 preparation is successively carried out preventing swollen performance, cytotoxicity and urgency
The performance evaluation of property toxicity etc..Since it is in all kinds of underground work liquid such as fracturing fluid, acid solution, perforating fluid and workover fluid
Dosage be 1~2wt.%, therefore only it is formulated as in following henchnmrk test 1~2wt.% solution respective performances into
Row evaluation.
(1) prevent swollen performance evaluation:
According to the Bohai Sea probing anti-dilative of current Q/SYBHZ0803~2009 detection method as standard, centrifugal process pair is used
Its anti-dilative is tested, i.e., by measuring in bentonite in powder respectively in the environmental protection of addition 1wt.%, 1.5wt.% and 2wt.%
After type clay stabilizer, and the bentonite in powder aqueous solution with different pH value is prepared, by the volume expansion for measuring bentonite in powder
Increment, to prevent that swollen performance is evaluated to the clay stabilizer；Wherein, experiment test temperature is 150 DEG C.
In this experiment, the calculation formula of anti-dilative are as follows: B=100* (V2~V1)/(V2~V0)；In formula, B is anti-for clay
Swollen rate, %；V0The volume for being bentonite in kerosene, mL；V1For volume of the bentonite in clay stabilization agent solution, mL；V2For
The volume of bentonite in water, mL.
Test result is as follows shown in table 1 for the anti-dilative of the clay stabilizer of Examples 1 to 4 preparation.
Table 1:
From the experimental result in table 1 it is found that Examples 1 to 4 preparation clay stabilizer 150 DEG C at a temperature of and 1~
Bentonitic anti-dilative reaches 88% or more within the scope of 14 pH, illustrate the clay stabilizer of the application show it is excellent
Prevent swollen performance.
In addition, after clay stabilizer prepared by Examples 1 to 4 is placed 30 days, 50 days, 100 days respectively, using above-mentioned phase
It is detected with method and prevents swollen performance, and test experiments result is consistent substantially with the test result in upper table 1, at 150 DEG C
At a temperature of and 1~14 pH within the scope of bentonitic anti-dilative still can achieve 88% or more, it is seen that it is disclosed in the present application viscous
Soil stabilizer prevents the swollen performance duration more than 1 month.
(2) Cytotoxic evaluation (MTT cell experiment)
The specific steps of experimental method are as follows: S1, cell kind plate: logarithmic growth phase is cells trypsinised, it prepares
At cell suspension, 96 orifice plates are inoculated in by 3000~5000 cell per wells, every hole adds 100 μ l, is placed in CO2(5%) in incubator
Overnight incubation is adherent at 37 DEG C, and edge hole is filled with sterile PBS；S2, added by the mass fraction preparation program listed in table 2
Medicine handles (experimental drug is clay stabilizer), and each concentration of specimens carries out 3~5 repetitions and tests；S3, MTT reaction: Suo Youkong
In be separately added into 20 μ lMTT solution (5mg/ml, i.e. 0.5%MTT), be incubated for 4 hours in incubator；S4, DMSO Rong Xie formazan: small
The absorption supernatant of the heart, every hole add 150 μ l of DMSO (dimethyl sulfoxide), shake at shaking table low speed (120~140rpm/min)
10min dissolves crystal sufficiently；S5, it surveys absorbance value: measuring 490nm absorbance value using microplate reader, count as follows
Clay stabilizer is calculated to the appreciation rate or survival rate of cell；Wherein, experimental period 72h.
In this experiment, the calculation formula of proliferation rate or survival rate A% are as follows: A (%)=100* (A1~A0)/(A2~A0)；
In formula, A1For the absorbance value of experimental group cell DMSO dissolution, A2For the absorbance value of cellular control unit DMSO dissolution, A0For
The absorbance value of DMSO solution.
The cytotoxicity test data of the clay stabilizer prepared in Examples 1 to 4 are as shown in table 2 below.
Table 2:
The method for recommending to evaluate cytotoxicity classification referring to standard GB/T/T16175~1996, cell proliferation rate >=
It is 0 grade when 100%, is 1 grade when 75~99%, 0 grade and 1 grade of toxic reaction are qualification.Therefore, from the test result in table 2
It is found that the cell survival rate of the clay stabilizer of different experiments concentration is fallen in 76~110% section, that is, illustrate clay stabilization
Agent does not have apparent cytotoxicity.
(3) acute toxicity is evaluated:
It is configured to respectively with every kind of clay stabilizer prepared by Examples 1 to 4 in above-mentioned Cytotoxic evaluation
The clay stabilizer aqueous solution of tri- kinds of mass fractions of 1wt.%, 1.5wt.% and 2wt.% carries out stomach-filling test to small white mouse, together
When observe small white mouse growth and survival condition.
The experimental results showed that half lethal concentration LC of the above-mentioned clay stabilizer aqueous solution to small white mouse50Range 11000~
15000mg/L illustrates that the clay stabilizer is less toxic or nontoxic.
In conclusion the clay stabilizer of Examples 1 to 4 preparation has both wide pH application environment, high temperature tolerance, height and prevents swollen property
And good biocompatibility.
Claims (9)
1. a kind of environment-friendlysticky sticky soil stabilizer, which is characterized in that including in parts by weight 5~30 portions of benzyl quaternary ammonium salt, 10~
30 parts of heterocycle polyquaterniums, 35~40 parts of sulphonyl quaternary ammonium salts and 5~40 parts of choline chlorides；Wherein, the benzyl quaternary ammonium salt is by N-
Amino ethyl ethanolamine, formaldehyde and benzyl chloride reaction are made；The heterocycle polyquaternium by N- amino ethyl ethanolamine, formaldehyde and
Dichloroether reaction is made；The sulphonyl quaternary ammonium salt is anti-by diethanol amine, formaldehyde, dithyl sulfate and bis- (diethanol amine) methane
It should be made.
2. environment-friendlysticky sticky soil stabilizer according to claim 1, which is characterized in that the benzyl quaternary ammonium salt is by 100~140
The benzyl chloride reaction of the N- amino ethyl ethanolamine of parts by weight, the formaldehyde of 60~75 parts by weight and 140~150 parts by weight is made.
3. environment-friendlysticky sticky soil stabilizer according to claim 1, which is characterized in that the preparation method of the benzyl quaternary ammonium salt
Are as follows: N- amino ethyl ethanolamine is added into the water of 2~2.5 times of N- amino ethyl ethanolamines and is stirred to being completely dissolved；
Under stirring condition, 30~45 DEG C are warming up to, formalin is added dropwise, 80~90 DEG C is warming up to after being added dropwise, then dropwise
Benzyl chloride is added, 80~90 DEG C of the reaction was continued 3~4h are kept after being added dropwise.
4. environment-friendlysticky sticky soil stabilizer according to claim 1, which is characterized in that the heterocycle polyquaternium includes 110
The dichloroether of the N- amino ethyl ethanolamine of~130 parts by weight, the formaldehyde of 65~75 parts by weight and 80~90 parts by weight.
5. environment-friendlysticky sticky soil stabilizer according to claim 1, which is characterized in that the preparation side of the heterocycle polyquaternium
Method are as follows: N- amino ethyl ethanolamine is added into the water of 2~3 times of N- amino ethyl ethanolamines and stirs to being completely dissolved；
Under stirring condition, 40~55 DEG C are warming up to, formalin is added dropwise, 80~90 DEG C is warming up to after being added dropwise, then dropwise
Dichloroether is added, 90~110 DEG C are warming up to after being added dropwise, the reaction was continued 16~20h.
6. environment-friendlysticky sticky soil stabilizer according to claim 5, which is characterized in that the rate of addition of the formalin
For 6~6.5g/min；The rate of addition of the dichloroether is 8~9g/min.
7. environment-friendlysticky sticky soil stabilizer according to claim 1, which is characterized in that the sulphonyl quaternary ammonium salt include 165~
The diethanol amine of 175 parts by weight, 22~26 parts by weight of formaldehyde, 240~260 parts sulfuric acid diethylesters and 25~35 parts by weight
Bis- (diethanol amine) methane.
8. environment-friendlysticky sticky soil stabilizer according to claim 1, which is characterized in that the preparation method of the sulphonyl quaternary ammonium salt
Are as follows: diethanol amine is added into the water of 1~1.5 times of diethanol amine and is stirred to being completely dissolved；Under stirring condition, it is warming up to
40~55 DEG C, formalin is added dropwise, 60~90 DEG C are warming up to after being added dropwise, then dithyl sulfate is added dropwise, drips
It is warming up to 100 DEG C after adding, adds bis- (diethanol amine) methane, the reaction was continued 10~12h.
9. environment-friendlysticky sticky soil stabilizer according to claim 8, which is characterized in that the rate of addition of the formalin
For 2~3g/min；The rate of addition of the dithyl sulfate is 1~1.5g/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811570053.1A CN109554171A (en) | 2018-12-21 | 2018-12-21 | Environment-friendlysticky sticky soil stabilizer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811570053.1A CN109554171A (en) | 2018-12-21 | 2018-12-21 | Environment-friendlysticky sticky soil stabilizer |
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| CN110105928A (en) * | 2019-05-08 | 2019-08-09 | 成都碧隆双田化工科技有限公司 | A kind of environment-friendlysticky sticky soil stabilizer of oil field low molecular weight and preparation method thereof |
| CN114106795A (en) * | 2022-01-29 | 2022-03-01 | 德仕能源科技集团股份有限公司 | Clay stabilizer, and preparation method and application thereof |
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