CN101921366B - Clay anti-swelling agent for oil extraction and preparation method thereof - Google Patents

Clay anti-swelling agent for oil extraction and preparation method thereof Download PDF

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CN101921366B
CN101921366B CN2009100866183A CN200910086618A CN101921366B CN 101921366 B CN101921366 B CN 101921366B CN 2009100866183 A CN2009100866183 A CN 2009100866183A CN 200910086618 A CN200910086618 A CN 200910086618A CN 101921366 B CN101921366 B CN 101921366B
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clay
swelling agent
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CN101921366A (en
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乔孟占
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Petrochina Co Ltd
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Petrochina Co Ltd
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Abstract

The invention relates to a clay anti-swelling agent for oil extraction and a preparation method thereof, according to the mass percentage, 50-90% of diallyl ammonium chloride monomer and 10-50% of triallylamine monomer are dissolved in distilled water, the total mass percentage concentration of the two monomers is 20-80%, the two monomers are added into a reaction kettle, nitrogen is introduced, an initiator is added at 65-85 ℃, the initiator is ammonium persulfate, potassium persulfate or hydrogen peroxide, and the reaction is carried out for 4-6 hours to obtain the clay anti-swelling agent for oil extraction of polymer with a molecular structure of three branched chains and containing organic cations; the anti-swelling agent has strong clay inhibition, durable anti-swelling effect, water flow scouring resistance and no damage to stratum, and can be used in water injection, acidification and well killing fluid.

Description

Clay antiswelling agent for petroleum extraction and preparation method thereof
Technical field
The present invention relates to employed oilfield chemistry agent-anti-clayswelling agent and preparation method thereof in a kind of oil and gas oil producing operation construction, be mainly used in water filling, acidifying and the well control fluid.
Background technology
The present anti-clayswelling agent (being called clay stabilizer again) that in the oil and gas exploitation construction, uses, product category is various, and conclude and get up to have several classes: 1. inorganic salts comprises Repone K, ammonium chloride, oxyaluminum, iron carbonyl etc.; 2. organic salt comprises Guanidinium hydrochloride, guanidine acetate, pyridinium salt, imidazoline salt etc.; 3. organic cation type polymer class comprises poly--2-hydroxypropyl alkyl dimethyl ammonium chloride, diallyl dimethyl ammoniumchloride, cationic polyacrylamide, epoxy chloropropionate alkene-polyethylene polyamine polycondensate, polyacrylamide propylene ethoxycarbonyl trimethyl ammonium chloride etc.The inorganic salts expansion-resisting agent is water-fast, and the stream performance of flushing is poor, and the organic salt expansion-resisting agent reduces the wetting ability of rock surface, makes the ability drop of water displacing oil.Organic cation type polymkeric substance heatproof, acidproof, oil resistant, validity period is long, and is anti-swollen effective.Its molecular structure of organic cation type expansion-resisting agent that uses is mainly straight chain or reticulated structure at present, and when molecular weight hour anti-swollen weak effect, throwing out can cause the stratum permeability injury when molecular weight is big, especially at middle low permeability reservoir.
Summary of the invention
The object of the present invention is to provide a kind of three branched structures, anti-swollen effective, do not injure stratum and anti-clayswelling agent with low cost and preparation method thereof.
Clay antiswelling agent for petroleum extraction of the present invention is to be made of diallyl ammonium chloride and the triallyl amine monomers mass percent by following component: diallyl ammonium chloride: triallylamine=50~90%: 10~50%.
The diallyl ammonium chloride monomer is diallyl ammonium chloride, diallyl-ammonio methacrylate, diallyldimethylammonium chloride or diallyl diethyl ammonium chloride.
The triallyl amine monomers is triallylamine, triallyl-methylamine or triallyl second.
Clay antiswelling agent for petroleum extraction of the present invention is to be made of diallyl ammonium chloride and the triallyl amine monomers mass percent in following ratio: diallyl ammonium chloride: triallylamine=50~90%: 10~50%.Two kinds of monomers are dissolved in the distilled water, and total concn is at 20~80% (mass percent concentrations), and optimum concn is 30~50%; Temperature of reaction is 10~100 ℃, and optimum temps is 65~85 ℃; Add initiator under nitrogen protection, initiator is a superoxide, and as ammonium persulphate, Potassium Persulphate or hydrogen peroxide, it is 0.01~0.1% of two kinds of monomer total masses that initiator adds quality.Polyreaction 1~20h, optimum reacting time are 4~6h, obtain a kind of clay antiswelling agent for petroleum extraction after polyreaction finishes, and its molecular structure is that three side chains contain organic cationic polymkeric substance.
Clay antiswelling agent for petroleum extraction of the present invention is a kind of cation type polymer of three side chains, overcome the deficiency of the anti-swollen weak effect of straight chain cation type polymer, overcome of the perviousness injury of netted cation type polymkeric substance to reservoir, be a kind of heatproof, acidproof, oil resistant, the anti-persistent anti-clayswelling agent of swollen effect, be used for the different measure operation of natural petroleum gas field process, as the anti-swollen processing of the particularly new converted production well of water injection well, spearhead in the acidification to dispel block operation, acidizing fluid and subsequent fluid, and in the well control fluid of using during the old and new's well operations.
Embodiment
Embodiment 1:
With 500ml glass reaction flask, install agitator, thermometer and inflated with nitrogen pipe add 200ml distilled water, 84g diallyldimethylammonium chloride and 14.5g triallylamine.Open and stir, fully dissolving feeds nitrogen fully, heat temperature raising, and adding the initiator initiator down at 75~80 ℃ is ammonium persulphate, and consumption is 0.03g, and polyreaction 4h obtains a kind of clay antiswelling agent for petroleum extraction.Its molecular structural formula is as follows:
Figure G2009100866183D00031
Embodiment 2:
With 500ml glass reaction flask, install agitator, thermometer and inflated with nitrogen pipe, add 220ml distilled water, 129g diallyl ammonium chloride and 21.5g triallyl quadrol are opened and are stirred, fully dissolving fully, feed nitrogen, heat temperature raising adds initiator down at 70~80 ℃, initiator is a Potassium Persulphate, consumption is 0.05g, and polyreaction 6h obtains a kind of clay antiswelling agent for petroleum extraction.Its molecular structural formula is as follows:
Figure G2009100866183D00032
Figure G2009100866183D00041
Wherein the chemical structural formula of B is:
Figure G2009100866183D00042
Embodiment 3:
With 500ml glass reaction flask, install agitator, thermometer and inflated with nitrogen pipe, add 220ml distilled water, 115g diallyl ammonium chloride and 24g triallylamine are opened and are stirred, fully dissolving fully, feed nitrogen, heat temperature raising adds initiator down at 75~80 ℃, initiator is hydrogen peroxide (its concentration is 30%), consumption is 0.4g, and polyreaction 5h obtains a kind of clay antiswelling agent for petroleum extraction.Its molecular structural formula is shown in embodiment 1.
Embodiment 4:
With 500ml glass reaction flask, install agitator, thermometer and inflated with nitrogen pipe, add 210ml distilled water, 135g diallyl diethyl ammonium chloride and 20.5g triallylamine are opened and are stirred, fully dissolving fully, feed nitrogen, heat temperature raising adds initiator down at 65~75 ℃, initiator is an ammonium persulphate, consumption is 0.05g, and polyreaction 5h obtains a kind of clay antiswelling agent for petroleum extraction.Its molecular structural formula is as follows:
Figure G2009100866183D00051
Use Anqiu wilkinite, according to SY/T5762-1995 " fracture acidizing clay stabilizer performance measurement method " and SY/T6486-2000 " water injection well acidifying medium clay soil is anti-swollen prevents the migration technological specification with particulate ", measure anti-swollen rate and 90 ℃ of scatter ratio, scatter and disappear ratios of several expansion-resisting agents, measurement result sees Table 1.
The anti-swollen rate of several expansion-resisting agents of table 1. and 90 ℃ of scatter ratio, scatter and disappear ratios
Expansion-resisting agent Example 1 sample Example 2 samples Example 3 samples Example 4 samples AQ-504 JD-1 FB-1
Anti-swollen rate, % 82.9 88.2 87.7 86.1 68.7 23.7 76.3
Scatter ratio, scatter and disappear ratio, % 18.97 12.11 18.02 15.9 21.18 13.14 40.91

Claims (1)

1. the preparation method of a clay antiswelling agent for petroleum extraction, it is characterized in that: by mass percentage, with 50~90% diallyl ammonium chloride monomers and 10~50% triallyl amine monomers, be dissolved in distilled water, two kinds of monomer total mass percentage concentrations are 20~80%, add in the reactor, feed nitrogen, at 65~85 ℃, add initiator, initiator is an ammonium persulphate, Potassium Persulphate or hydrogen peroxide, reaction 4~6h, obtaining molecular structure is that three side chains contain organic cationic polymkeric substance clay antiswelling agent for petroleum extraction, and it is 0.01~0.1% of two kinds of monomer total masses that initiator adds quality.
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CN104861110B (en) * 2015-05-22 2016-09-07 中国石油集团渤海钻探工程有限公司 Thief zone heavy crude reservoir is prevented swollen pressing down sand agent and preparation method thereof
CN106467735B (en) * 2015-08-21 2019-02-19 中国石油化工股份有限公司 A kind of clay stabilizer and preparation method thereof for slippery water fracturing fluid
CN105754576A (en) * 2015-12-28 2016-07-13 重庆地质矿产研究院 Anti-swelling agent for shale gas slickwater fracturing fluid and preparation method thereof
CN106351063B (en) * 2016-08-19 2018-03-13 浙江恒达新材料股份有限公司 A kind of dispersed copolymer of organic boron multiple crosslinking agent and cationic polymer and its preparation method and application, papermaking process
CN110358510B (en) * 2019-07-16 2021-08-17 荆州市众天化工有限公司 Strong-sensitive anti-swelling inhibitor for continental facies shale and preparation method thereof

Citations (2)

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US4374739A (en) * 1976-08-13 1983-02-22 Halliburton Company Oil well treating method and composition
CN1483750A (en) * 2002-09-20 2004-03-24 凯 党 Cation polymer and expansion-resisting agent containing same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4374739A (en) * 1976-08-13 1983-02-22 Halliburton Company Oil well treating method and composition
CN1483750A (en) * 2002-09-20 2004-03-24 凯 党 Cation polymer and expansion-resisting agent containing same

Non-Patent Citations (1)

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范振中等.注水用粘土稳定剂FL-1的研制与应用.《精细石油化工进展》.2005,第6卷(第10期),第9-11页. *

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