CN109439292A - Clay stabilizer - Google Patents
Clay stabilizer Download PDFInfo
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- CN109439292A CN109439292A CN201811231921.3A CN201811231921A CN109439292A CN 109439292 A CN109439292 A CN 109439292A CN 201811231921 A CN201811231921 A CN 201811231921A CN 109439292 A CN109439292 A CN 109439292A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/02—Well-drilling compositions
- C09K8/03—Specific additives for general use in well-drilling compositions
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- 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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- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
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Abstract
A kind of clay stabilizer includes: 20-25 parts of polyether polyol by weight；40% 5-7 parts of potassium hydroxide solution；5-9 parts of epoxychloropropane；10-15 parts of polyethylene polyamine；6-10 parts of glacial acetic acid；25-40 parts of deionized water；8-10 parts of dodecyl benzyl dimethyl ammonium chloride；5-15 parts of hydroxy Al.The invention proposes a kind of preparation method of small cation polymer, the clay stabilizer which is compounded with dodecyl benzyl dimethyl ammonium chloride, hydroxy Al has long-term effect good, and resistance to erosion will not block less permeable layer.
Description
Technical field
The present invention relates to reservoir protection technical field more particularly to a kind of clay stabilizers.
Background technique
As oil field is continually developed, reservoir protection technology is increasingly attracted people's attention.The high, water sensitivity to clay content
Strong reservoir, in any technological measure such as drilling well, well cementation, water filling, pressure break, acidification, well workover and kill-job, as long as there is water base work
The intrusion of liquid, is likely to cause water fire extinguishing, the use of clay stabilizer is the effective hand for protecting water-sensitive formation in oil layer protection
Therefore, research function admirable, adaptable clay stabilizer have important justice to section.
Inorganic salts clay stabilizer is in oil recovery process, with the dilution of injection water or other secondary waters, in water flooding
Na+ will replace K+ again, with the increase of dilute strength, effect is gradually deteriorated, K+ concentration reduce to a certain extent when stablize
The effect of clay will disappear, and this kind of clay stabilizer can not generate multiple spot absorption as polymer, therefore to preventing from gluing
Soil migration effect is unobvious.This kind of stabilizer is used primarily in the operations such as drilling well, pressure break, acidification.Its feature: mainly price is low
Honest and clean, short-term preventive effect of expansion is good, but its disadvantage is also extremely obvious, prevents that swollen validity period is short, and poor to inhibition fine migration effect.
Its mechanism of inorganic cationic polymer be trivalent and trivalent or more metal ion (Al3+, Cr3+, Zr3+, Zr4+,
Ti4+), these inorganic cation type polymer can dissociate polynuclear hydroxy bridge complex ion in water.Due to polynuclear hydroxy bridge complex ion
There is very high positive electricity price and structure is similar to clay, so energy adsorbed close reduces its negative electricity on the electronegative surface of clay
Property.To effectively inhibit clay swell.In addition, polynuclear hydroxy bridge complex ion can be by the electronegative small bits of clay in surface and with negative
The surface of stratum of electricity is bridged and fixes particle, prevents fine migration.Its advantage is that preventing swollen validity period compared with salt and cation
Type surfactant is all long, the disadvantage is that acid resistance is poor, is not suitable for the high stratum of carbonate content.
Organic clay stabilizer can more securely adsorbing clays particle, be not easy by other ionic compartmentations, long-term effect is good,
Resistance to erosion.But molecular weight is excessive, and improper use can block low permeability reservoir pore throat instead, reduces reservoir permeability.
China Patent Publication No.: CN107760283 discloses a kind of oil field clay stabilizer, constituent content quality hundred
Distribution ratio are as follows: ammonium chloride 3%-12%, small cation surfactant 15%-25%, isopropanol 3%-10%, inorganic salts 1%-
5%, deionized water 60%-70%.It can be seen that the oil field is had the following problems with clay stabilizer:
First, using strong acid production isopropanol in a kind of carcinogenic substance inventory, isopropanol in 3 class carcinogenic substance inventories, it is high
There is concentration vapor obvious anesthetic effect can damage retina and optic nerve to the irritating effect of the mucous membrane of eye, respiratory tract.It connects
It touches high concentration steam and headache, drowsiness and eye, nose, larynx irritation occurs.Eat or suck a large amount of steam can cause it is flushing,
Headache, mental depression, nausea, stupor.
Second, ammonium chloride is irritant to skin, mucous membrane, can cause liver and kidney dysfunction, induces hepatic coma, causes nitrogen matter
Mass formed by blood stasis and metabolic acidosis etc..Healthy People application 50g ammonium chloride can cause severe intoxication, there is hepatopathy, nephrosis, morbus cardiacus
Patient, 5g can cause seriously to be poisoned.Oral ingestion causes chemical gastritis, and serious person induces liver since blood ammonia significantly increases
Stupor.Liver, renal damage are caused when serious poisoning, metabolic acidosis occurs, while bronchial secretion increases significantly.Occupational
Contact, can cause the stimulation of respiratory mucosa and burn.Chronic Effect: regular contact ammonium chloride can cause eye conjunctiva and exhale
Inhale road mucous membrane chronic inflammation.
Third, the clay stabilizer molecular weight is excessive, and improper use can block low permeability reservoir pore throat, reduces reservoir and seeps
Saturating rate.
Summary of the invention
For this purpose, the present invention provides a kind of clay stabilizer, to overcome the problems, such as that stability is low in the prior art.
On the one hand, the present invention provides a kind of clay stabilizer, includes: by weight
Further, the clay stabilizer includes: 20 parts of polyether polyol by weight；40% potassium hydroxide solution 5
Part；5 parts of epoxychloropropane；10 parts of polyethylene polyamine；6 parts of glacial acetic acid；25 parts of deionized water；Dodecyl dimethyl Benzylmagnesium chloride
8 parts of ammonium；5 parts of hydroxy Al.
Further, the clay stabilizer includes: 25 parts of polyether polyol by weight；40% potassium hydroxide solution 7
Part；9 parts of epoxychloropropane；15 parts of polyethylene polyamine；10 parts of glacial acetic acid；40 parts of deionized water；Dodecyl dimethyl benzyl chloride
Change 10 parts of ammonium；15 parts of hydroxy Al.
Further, the clay stabilizer includes: 22 parts of polyether polyol by weight；40% potassium hydroxide solution 6
Part；7 parts of epoxychloropropane；12 parts of polyethylene polyamine；8 parts of glacial acetic acid；30 parts of deionized water；Dodecyl dimethyl Benzylmagnesium chloride
9 parts of ammonium；13 parts of hydroxy Al.
On the other hand, the present invention provides a kind of production methods of clay stabilizer, comprising:
Step 1: pure and mild 40% potassium hydroxide solution of the polyether polyols of specified wt part being sequentially added into reaction kettle, is stirred
Mix uniformly after heating, heating after the completion of be added specified wt part epoxychloropropane and polyethylene polyamine and to reaction kettle carry out into
One step heating, after the completion of heating, to reaction kettle be added specified wt part glacial acetic acid continue stirring until reaction kettle be down to room temperature,
Obtain thick small cation polymer.
Step 2: the small cation polymer in the step 1 being added in reaction kettle, is sequentially added under agitation
The deionized water, dodecyl benzyl dimethyl ammonium chloride and hydroxy Al hydroxy Al of specified wt part simultaneously stir, and obtain described viscous
Soil stabilizer.
Further, in the step 1, it is 45-50 DEG C that the temperature to heat up after 40% sodium hydroxide is added to reaction kettle.
Further, in the step 1, the temperature to heat up after epoxychloropropane and polyethylene polyamine is added to reaction kettle
It is 60-70 DEG C.
Further, the mixing time after being warming up to 60-70 DEG C is 2h.
Further, in the step 1, the mixing time after glacial acetic acid is added to reaction kettle is 2h.
Further, the mixing time in the step 2 is 30min.
Compared with prior art, the beneficial effects of the present invention are the invention proposes a kind of small cation polymer
Preparation method, the clay stabilizer tool which is compounded with dodecyl benzyl dimethyl ammonium chloride, hydroxy Al
Have that long-term effect is good, it is resistance to wash away, less permeable layer will not be blocked.
Further, each component effect is as follows in the present invention:
Polyether polyol: being that main chain contains ehter bond, end group or side group contain the oligomer greater than 2 hydroxyls.It is with low point
Sub- weight polyalcohol, polyamine or the compound containing active hydrogen are initiator, with oxyalkylene ring-opening polymerisation under the action of catalyst
It forms.It can be used as detergent, defoaming agent, excipient, emulsifier, wetting agent, antistatic agent, dispersing agent, demulsifier, paper making additive
Deng
40% potassium hydroxide solution: white powder or chip solid, 380 DEG C of fusing point, 1324 DEG C of boiling point, relative density
2.04g/cm3, there is strong basicity and corrosivity.It easily absorbs moisture in air and deliquesces, absorbing carbon dioxide forms potassium carbonate.
Amount of heat is generated when being dissolved in water, alcohol or being handled with acid, has extremely strong alkalinity and corrosivity, property similar to caustic soda.
As desiccant, absorbent, for oxalic acid processed and various sylvite；The raw material of sylvite production；Chemical industry base stock；For medicine,
Daily-use chemical industry etc.；Absorbent as analytical reagent, saponification reagent, carbon dioxide and moisture.
Epoxychloropropane: it is mainly applicable in epoxy resin processed and a kind of stabilizer of oxygen carrier and chemistry
The primary raw material of mesosome, epoxy group and phenoxy resin；Manufacture glycerol；Cure propylene-based rubber；The solvent of cellulose esters and ether；
The high wet-strength resins of paper industry.
Polyethylene polyamine: polyethylene polyamine is the coproduction of ethylenediamine, diethylenetriamine, triethylene tetramine and tetraethylenepentamine
Object.It is yellow or transparent salmon thick liquid, there is ammonia odor.Easily absorb the moisture and carbon dioxide in air.It is raw with acid
At corresponding salt, when low temperature, can solidify.In strong basicity.It can be miscible with water, pure and mild ether.It is corrosive.It is characterized in that strand
In simultaneously there are the structures such as amido, polyoxyethylene (or polyoxypropylene), organosilicon oxygen, multi-arm, combine their excellent properties,
With good surface-active and temperature-resistance characteristic.It is mainly used as epoxy curing agent, crude oil demulsifier, mining auxiliary agent, lubricating grease
Additive, bentonite lubricant, cyanideless electro-plating additive and it is used to prepare ion exchange resin.
Glacial acetic acid: i.e. anhydrous acetic acid, acetic acid are important one of organic acid, organic compound.It is frozen into low temperature
Ice-like is commonly called as glacial acetic acid.Volume expansion may cause vessel breaks when solidification.39 DEG C of flash-point, explosion limit 4.0%~
16.0%, maximum acceptable concentration is no more than 25mg/m3 in air.Be mainly used for synthesizing vinyl acetate, acetate fiber, acetic anhydride,
Acetate, metal acetate salt and halogenated acetic acid etc..It is also the important source material of pharmacy, dyestuff, pesticide and other organic syntheses.This
Outside, the manufacture of photograph drug, cellulose acetate, fabric printing and in terms of also have been widely used, manufacture modeling
Material, the solvent of dyestuff, photograph, medicine, pesticide and the raw material of other organic syntheses.
Deionized water: refer to the pure water eliminated in after ionic species impurity.It is mainly used for laboratory, laboratory water, one
As laboratory routine test, configuration stock solution, cleaning glassware；Electronics industry production, such as picture tube glass bulb, imaging
Pipe, liquid crystal display, wiring board, hard disc of computer, IC chip, single-crystal semiconductor；Electric boiler is soft needed for boiler
Change water, desalination；Automobile, household electrical appliance, building material surface coating, plating, coated glass cleaning；Petrochemical industry, chemical reaction
Liquid water is matched in cooling water, chemical agent, production；Industrial textile printing and dyeing, steel water for cleaning；Food, beverage, drinks, cosmetics
Industrial water；The purification such as seawater and brackish water.
Dodecyl benzyl dimethyl ammonium chloride: being a kind of cationic surfactant, belongs to non oxidizing bactericide, has
Wide spectrum, efficient sterilization algae removal ability can efficiently control bacterium algae breeding and foundry loam growth in water, and have the stripping of good foundry loam
From effect and certain dispersion, osmosis, at the same have it is certain deoil, deodorizing capability and corrosion inhibition.It is widely used in
In the recirculating cooling water system of the industries such as petroleum, chemical industry, electric power, weaving, bred to control loop cooling water system bacterium algae, it is right
Killing sulfate reducing bacteria has special efficacy.Also biocide mildewcide and softening agent, antistatic agent, the emulsification of textile printing and dyeing industry be can be used as
Agent, conditioner etc..
Specific embodiment
In order to which objects and advantages of the present invention are more clearly understood, the present invention is further retouched below with reference to embodiment
It states；It should be appreciated that specific embodiment described herein is used only for explaining the present invention, it is not intended to limit the present invention.
The embodiment of the present invention is with polyether polyol, 40% potassium hydroxide solution, epoxychloropropane, polyethylene polyamine, ice second
Acid, deionized water, dodecyl benzyl dimethyl ammonium chloride, hydroxy Al are raw material, are matched below according to each embodiment is different
Than being illustrated.
Embodiment 1
A kind of clay stabilizer includes 20 parts of polyether polyol by weight；40% 5 parts of potassium hydroxide solution；Epoxy
5 parts of chloropropane；10 parts of polyethylene polyamine；6 parts of glacial acetic acid；25 parts of deionized water；8 parts of dodecyl benzyl dimethyl ammonium chloride；
5 parts of hydroxy Al.
The production method of the clay stabilizer includes:
Step 1: pure and mild 40% potassium hydroxide solution of polyether polyols being sequentially added into reaction kettle, is heated after mixing evenly
Epoxychloropropane and polyethylene polyamine are added to 45 DEG C, after the completion of heating and 60 DEG C and the reaction was continued 2h are heated to reaction kettle,
After the completion of heating, to reaction kettle be added glacial acetic acid continue stir 2h until reaction kettle be down to room temperature, obtain thick small cation
Polymer.
Step 2: the small cation polymer in the step 1 being added in reaction kettle, is sequentially added under agitation
Deionized water, dodecyl benzyl dimethyl ammonium chloride and hydroxy Al hydroxy Al simultaneously stir 30min, obtain the clay stabilization
Agent.
Embodiment 2
A kind of clay stabilizer includes 25 parts of polyether polyol by weight；40% 7 parts of potassium hydroxide solution；Epoxy
9 parts of chloropropane；15 parts of polyethylene polyamine；10 parts of glacial acetic acid；40 parts of deionized water；Dodecyl benzyl dimethyl ammonium chloride 10
Part；15 parts of hydroxy Al.
The production method of the clay stabilizer includes:
Step 1: pure and mild 40% potassium hydroxide solution of polyether polyols being sequentially added into reaction kettle, is heated after mixing evenly
Epoxychloropropane and polyethylene polyamine are added to 50 DEG C, after the completion of heating and 70 DEG C and the reaction was continued 2h are heated to reaction kettle,
After the completion of heating, to reaction kettle be added glacial acetic acid continue stir 2h until reaction kettle be down to room temperature, obtain thick small cation
Polymer.
Step 2: the small cation polymer in the step 1 being added in reaction kettle, is sequentially added under agitation
Deionized water, dodecyl benzyl dimethyl ammonium chloride and hydroxy Al hydroxy Al simultaneously stir 30min, obtain the clay stabilization
Agent.
Embodiment 3
A kind of clay stabilizer includes 22 parts of polyether polyol by weight；40% 6 parts of potassium hydroxide solution；Epoxy
7 parts of chloropropane；12 parts of polyethylene polyamine；8 parts of glacial acetic acid；30 parts of deionized water；9 parts of dodecyl benzyl dimethyl ammonium chloride；
13 parts of hydroxy Al.
The production method of the clay stabilizer includes:
Step 1: pure and mild 40% potassium hydroxide solution of polyether polyols being sequentially added into reaction kettle, is heated after mixing evenly
Epoxychloropropane and polyethylene polyamine are added to 48 DEG C, after the completion of heating and 65 DEG C and the reaction was continued 2h are heated to reaction kettle,
After the completion of heating, to reaction kettle be added glacial acetic acid continue stir 2h until reaction kettle be down to room temperature, obtain thick small cation
Polymer.
Step 2: the small cation polymer in the step 1 being added in reaction kettle, is sequentially added under agitation
Deionized water, dodecyl benzyl dimethyl ammonium chloride and hydroxy Al hydroxy Al simultaneously stir 30min, obtain the clay stabilization
Agent.
According to the acidification of SY/T 5971-2016 oil-gas field fracturing and water filling with clay stabilizer method of evaluating performance to implementation
It is as shown in table 1 that example A, B, C and commercial product carry out Evaluation results:
Table 1
According to table 1 it can be seen that anti-dilative and water-fastness ability are superior to presently commercially available routine in various embodiments of the present invention
Clay stabilizer.
The above description is only a preferred embodiment of the present invention, is not intended to restrict the invention；For those skilled in the art
For member, the invention may be variously modified and varied.All within the spirits and principles of the present invention, it is made it is any modification,
Equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of clay stabilizer, which is characterized in that include: by weight
2. clay stabilizer according to claim 1, which is characterized in that by weight include: 20 parts of polyether polyol；
40% 5 parts of potassium hydroxide solution；5 parts of epoxychloropropane；10 parts of polyethylene polyamine；6 parts of glacial acetic acid；25 parts of deionized water；12
8 parts of zephiran；5 parts of hydroxy Al.
3. clay stabilizer according to claim 1, which is characterized in that by weight include: 25 parts of polyether polyol；
40% 7 parts of potassium hydroxide solution；9 parts of epoxychloropropane；15 parts of polyethylene polyamine；10 parts of glacial acetic acid；40 parts of deionized water；12
10 parts of zephiran；15 parts of hydroxy Al.
4. clay stabilizer according to claim 1, which is characterized in that by weight include: 22 parts of polyether polyol；
40% 6 parts of potassium hydroxide solution；7 parts of epoxychloropropane；12 parts of polyethylene polyamine；8 parts of glacial acetic acid；30 parts of deionized water；12
9 parts of zephiran；13 parts of hydroxy Al.
5. a kind of production method of clay stabilizer characterized by comprising
Step 1: pure and mild 40% potassium hydroxide solution of the polyether polyols of specified wt part being sequentially added into reaction kettle, stirring is equal
Heating after even is heated the epoxychloropropane that specified wt part is added after the completion and polyethylene polyamine and is carried out to reaction kettle further
Heating, after the completion of heating, to reaction kettle be added specified wt part glacial acetic acid continue stirring until reaction kettle be down to room temperature, obtain
Thick small cation polymer.
Step 2: the small cation polymer in the step 1 being added in reaction kettle, is sequentially added under agitation specified
Deionized water, dodecyl benzyl dimethyl ammonium chloride and the hydroxy Al of parts by weight simultaneously stir, and obtain the clay stabilizer.
6. the production method of clay stabilizer according to claim 5, which is characterized in that in the step 1, to reaction kettle
It is 45-50 DEG C that the temperature to heat up after 40% sodium hydroxide, which is added,.
7. the production method of clay stabilizer according to claim 5, which is characterized in that in the step 1, to reaction kettle
It is 60-70 DEG C that the temperature to heat up after epoxychloropropane and polyethylene polyamine, which is added,.
8. the production method of clay stabilizer according to claim 7, which is characterized in that the stirring after being warming up to 60-70 DEG C
Time is 2h.
9. the production method of clay stabilizer according to claim 5, which is characterized in that in the step 1, to reaction kettle
Mixing time after glacial acetic acid is added is 2h.
10. the production method of clay stabilizer according to claim 5, which is characterized in that when stirring in the step 2
Between be 30min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811231921.3A CN109439292A (en) | 2018-10-22 | 2018-10-22 | Clay stabilizer |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811231921.3A CN109439292A (en) | 2018-10-22 | 2018-10-22 | Clay stabilizer |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110551488A (en) * | 2019-10-11 | 2019-12-10 | 北京宏勤石油助剂有限公司 | clay inhibitor for drilling fluid and preparation method thereof |
| CN112169621A (en) * | 2020-09-16 | 2021-01-05 | 郑州德融科技有限公司 | Clay stabilizer and preparation method thereof |
| CN112745233A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Small-molecule clay stabilizer suitable for low-permeability oil reservoir and preparation method thereof |
| CN113563859A (en) * | 2021-07-16 | 2021-10-29 | 济南雅歌新材料科技有限公司 | Use of carbon-rich fluids for enhanced oil recovery |
| CN114989799A (en) * | 2022-07-18 | 2022-09-02 | 华巍博大(北京)科技有限公司 | Oligomeric cationic type shrinkage-swelling agent composition, oligomeric cationic type shrinkage-swelling agent, and preparation method and application thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110551488A (en) * | 2019-10-11 | 2019-12-10 | 北京宏勤石油助剂有限公司 | clay inhibitor for drilling fluid and preparation method thereof |
| CN110551488B (en) * | 2019-10-11 | 2021-11-09 | 北京宏勤石油助剂有限公司 | Clay inhibitor for drilling fluid and preparation method thereof |
| CN112745233A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Small-molecule clay stabilizer suitable for low-permeability oil reservoir and preparation method thereof |
| CN112169621A (en) * | 2020-09-16 | 2021-01-05 | 郑州德融科技有限公司 | Clay stabilizer and preparation method thereof |
| CN113563859A (en) * | 2021-07-16 | 2021-10-29 | 济南雅歌新材料科技有限公司 | Use of carbon-rich fluids for enhanced oil recovery |
| CN114989799A (en) * | 2022-07-18 | 2022-09-02 | 华巍博大(北京)科技有限公司 | Oligomeric cationic type shrinkage-swelling agent composition, oligomeric cationic type shrinkage-swelling agent, and preparation method and application thereof |
| CN114989799B (en) * | 2022-07-18 | 2022-10-25 | 华巍博大(北京)科技有限公司 | Oligomeric cationic shrinking and swelling agent composition, oligomeric cationic shrinking and swelling agent, and preparation method and application thereof |
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