CN104140454B - A kind of drilling fluid polyethers amido APG and preparation method thereof - Google Patents
A kind of drilling fluid polyethers amido APG and preparation method thereof Download PDFInfo
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- CN104140454B CN104140454B CN201310523186.4A CN201310523186A CN104140454B CN 104140454 B CN104140454 B CN 104140454B CN 201310523186 A CN201310523186 A CN 201310523186A CN 104140454 B CN104140454 B CN 104140454B
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Abstract
The invention discloses a kind of drilling fluid polyethers amido APG and preparation method thereof, belong to oilfield chemistry additive for drilling fluid technical field.Step is as follows：（1）It is in molar ratio 1 by epoxides, APG, water, catalyst:0.5~1：4~8:0.01~0.10 adds autoclave, starts stirring, and 0.5~4.0h is reacted at 3~10MPa, 50~110 DEG C of temperature, obtains the aqueous solution of APG polyethers；（2）It is 6~9 that the aqueous solution nertralizer of abovementioned alkyl glucosides polyethers is neutralized to pH value, adds organic amine, and APG polyethers is in molar ratio 1 with organic amine：0.8~1.2 mixing, in 40~90 DEG C of temperature, 3~10h of synthesis under normal pressure, obtains the polyethers amido APG aqueous solution of Chinese red clear viscous, and water removal obtains final product polyethers amido APG product.Its shale inhibition can be excellent, and 150 DEG C of high temperature roll 16h, shale primary recovery ＞ 97%, relative recovery ＞ 99% in the polyethers amido APG aqueous solution that concentration is 1%.
Description
Technical field
The present invention relates to a kind of APG derivative and preparation method thereof, more particularly to a kind of polyethers aminoalkyl sugar
Glycosides and preparation method thereof, belongs to oilfield chemistry additive for drilling fluid technical field.
Background technology
Polyetheramine is the tough curing agent of a based epoxy resin and prepares the primary raw material of Polyurethane urea and polyurea materials, closely
Year is used as a kind of potent inhibitor and starts to be applied in drilling fluid.It is applied to show advantages below in drilling fluid：（1）Can be with
Suppress most of active shale, there is provided good borehole wall stability；（2）Low shear thinning rate, is conducive to improving ratio of dynamic shear force/yield value to plastic viscosity, with
Suspension drilling cuttings ability is improved, prevents landwaste from depositing, it is to avoid the generation of the various accidents in underground；（3）Anti- mud drum ability is strong, lubricity
It is good, be conducive to improving drilling speed, beneficial to well cleaning；（4）Rheological characteristic is good, and solid concentration is low, and contamination resistance is strong；（5）Can be biological
Degradability is strong, is conducive to environmental protection；（6）Salt-resistance is strong, can be used for the saline formulation of various concentrations, in deep ocean work can in case
Only drilling fluid produces bubble.But it there is also dosage greatly, and heat-resisting property is relatively poor, the shortcoming of high cost.Application No.
201210052388.0 patent discloses a kind of preparation method of polyetheramine, and main chain is PPOX, PEO, gathers
Tetrahydrofuran or the copolymer of three, one end of main chain is hydroxyl, and the other end of main chain is with NH2The alcohol of-R-OH structures
Aminated compounds is blocked.Using tertbutyloxycarbonyl（BOC）Protect the amido of alcamine compound, hydroxyl to retain, obtain BOC-NH-
R-OH；BOC-NH-R-OH highly basic or it is double metal cyanide-catalyzed under, trigger oxirane, expoxy propane, tetrahydrofuran or
The mixture reaction of person three, carries out ring-opening polymerisation；In acid condition, the deprotection reaction of BOC is carried out, polyetheramine is obtained.
The invention can obtain the polyethers of different hydrophilic by adjusting polyether chain oxypropylene, oxirane and the ratio of tetrahydrofuran
Amido is contained in main chain, one end of polyether chain, and stronger hydrophily can be provided after acidifying, can be applied to surfactant, flocculation
The fields such as agent, dyeing and finishing auxiliaries and electrophoretic paint.The patent of Application No. 201310095868.X disclose a kind of polyetheramine and its
Preparation method, the invention is protected using ketone or aldehydes or acid anhydrides with primary amine groups reaction generation ketimide or aldimine or acyl group first
The aminated compounds of shield, anionic polymerisation is carried out with secondary amine or active hydroxyl groups with alkylene oxides monomer, and synthesis is poly- containing primary amine groups
Ether amines.The invention overcomes conventional method hydroxyl direct aminatin to the requirement of the critical conditions of equipment and technique, aminated compounds with
Easily there is the defect such as side reaction when polyether chain is connected, successfully synthesize that reaction condition is gentle, the polyetheramine of compound with regular structure.
APG is mainly used in the multiple industry such as daily chemical products, weaving, leather agent, paper making additive, 20th century 90
Age starts to be applied to drilling fluid.The report for being applied to drilling fluid earliest appears in what is held in dallas, U.S.A within 1994
IADC in SPE drilling engineering meetings, achievement in research causes the extensive concern of participant.Afterwards, domestic petroleum university（Beijing）
And University of Petroleum（East China）And other research institutions have carried out correlative study in succession, by the development of more than ten years, achieve larger
Progress.Current methyl glucoside drilling fluid has formed the system of comparative maturity, there is many reports for being successfully applied to scene,
But there is the defect that dosage is big, rejection and heat-resisting property have much room for improvement, above-mentioned deficiency limits it and enters one in drilling fluid
Step application.Patent CN 200910112354.4 discloses a kind of preparation method of methyl glucoside, with cellulose and first
Alcohol is raw material, and with methyl alcohol as reaction medium, in the presence of acidic, cellulose and methanol oxidation reaction directly prepare methyl
Glucoside.Whole technical process is simple, and methyl glucoside highest yield can reach 65%.
Though polyetheramine is applied to having many advantages, such as there is dosage greatly in drilling fluid, heat-resisting property is relatively poor, into
This shortcoming high.APG is applied in drilling fluid to exist the defect that dosage is big, rejection and heat-resisting property have much room for improvement.
The content of the invention
Polyetheramine and APG the invention aims to overcome above-mentioned prior art to exist are applied to drilling fluid
In there is the defects such as dosage is big, heat-resisting property is relatively poor, a kind of page that the synthesis of polyethers amido is introduced on APG is provided
Rock inhibitor polyethers amido APG.It is a further object to provide a kind of reaction condition is gentle, technological operation is simple
Single drilling fluid polyethers amido APG preparation method.
A kind of drilling fluid polyethers amido APG, its general structure is：
In formula：m=0,1,2,3,4,5；n=0,1,2,3,4,5；o=0,1,2,3；R=-CH3,-C2H5,-C3H6,-C4H8.
Molecular weight ranges are：252.18~934.44.
The present invention is comprised the following steps that：
（1）It is in molar ratio 1 by epoxides, APG, water, catalyst:0.5~1：4~8:0.01~0.10 adds
Enter autoclave, start stirring, 0.5~4.0h is reacted at 3~10MPa, 50~110 DEG C of temperature, obtain APG polyethers
The aqueous solution；
（2）It is 6~9 that the aqueous solution nertralizer of abovementioned alkyl glucosides polyethers is neutralized to pH value, adds organic amine, alkyl
Glucosides polyethers is in molar ratio 1 with organic amine：0.8~1.2 mixing, in 40~90 DEG C of temperature, 3~10h of synthesis under normal pressure, obtains tangerine
The sticky polyethers amido APG aqueous solution of red, transparent, water removal obtains final product polyethers amido APG product.
Described epoxides be oxirane, expoxy propane in one or two；
Described catalyst is the mixture of the compounding of inorganic acid, organic acid or inorganic acid and organic acid；
Described inorganic acid is the one kind in sulfuric acid, nitric acid, phosphoric acid, phosphotungstic acid；
Described organic acid is the one kind in p-methyl benzenesulfonic acid, DBSA, sulfamic acid.
Described APG is the one kind in methylglycoside, ethyl glucoside, propyl glucoside, butyl glycoside；
Described nertralizer is the one kind in NaOH, KOH, Na2CO3；
Described organic amine is the one kind in ethylenediamine, diethylenetriamine, triethylene tetramine, TEPA.
The beneficial effects of the invention are as follows：
The present invention uses APG, epoxides and organic amine that polyethers amido APG is prepared for raw material, reacts bar
Part is gentle, and technological operation is simple, and sintetics environmental protection, product is a kind of excellent shale-control agent for drilling fluid.
Specific embodiment：
Embodiment 1
In equipped with thermometer, condenser pipe, the autoclave of agitator, add oxirane 44.05g, methylglycoside 97g,
Distilled water 72g and p-methyl benzenesulfonic acid 1.72g, 0.5h is reacted under 3MPa, temperature 50 C, obtains the water-soluble of methylglycoside polyethers
Liquid；It is 6 that the aqueous solution nertralizer of above-mentioned methylglycoside polyethers is neutralized to pH value, adds ethylenediamine 24g, 40 DEG C of temperature,
3h is reacted under normal pressure, the liquid of Chinese red clear viscous is obtained, water removal obtains final product polyethers aminomethyl glycoside products.Shale is in concentration
For 150 DEG C of high temperature roll 16h in the 1% polyethers aminomethyl glucosides aqueous solution, shale primary recovery 97.14% is relative to reclaim
Rate 99.45%.
A kind of drilling fluid polyethers amido APG is obtained, its structural formula is：
In formula：m=0,1,2,3,4,5.
The step of embodiment 2~8 is same as Example 1, obtains formula：
In formula：m=0,1,2,3,4,5；n=0,1,2,3,4,5；o=0,1,2,3；R=-CH3,-C2H5,-C3H6,-C4H8.
Molecular weight ranges are：252.18~934.44.
Specific reactive material, reaction condition and properties of product are as shown in table 1：
The reactive material consumption of table 1, reaction condition and properties of product table
The shale inhibition of the polyethers amido APG product prepared in embodiment 1~8 can be as shown in table 2：
The shale of table 2 is in 1% embodiment product aqueous solution high temperature rolling rate of recovery
Note：R1：Shale primary recovery, R：Shale relative recovery.
As shown in Table 1, compared with prior art, reaction condition is gentle for the present invention, and technological operation is simple, sintetics green
Environmental protection.The polyethers amido APG product that the present invention synthesizes is a kind of excellent shale-control agent for drilling fluid.Can by table 2
Know, shale 150 DEG C of high temperature in the polyethers amido APG aqueous solution that concentration is 1% roll 16h, shale primary recovery ＞
97%, relative recovery ＞ 99%.
Claims (5)
1. a kind of drilling fluid polyethers amido APG, it is characterized in that：Its general structure is：
In formula：M=0,1,2,3,4,5 in formula；N=0,1,2,3,4,5；O=0,1,2,3；R=-CH3,-C2H5,-C3H7,-C4H9,
Molecular weight ranges are：252.18~934.44.
2. a kind of drilling fluid as claimed in claim 1 preparation method of polyethers amido APG, it is characterised in that including
Following steps：
(1) it is in molar ratio 1 by epoxides, APG, water, catalyst:0.5~1：4~8:0.01~0.10 adds height
Pressure kettle, starts stirring, and 0.5~4.0h is reacted at 3~10MPa, 50~110 DEG C of temperature, obtains the water-soluble of APG polyethers
Liquid；
(2) it is 6~9 to neutralize to pH value the aqueous solution nertralizer of abovementioned alkyl glucosides polyethers, adds organic amine, APG
Polyethers is in molar ratio 1 with organic amine：0.8~1.2 mixing, in 40~90 DEG C of temperature, 3~10h of synthesis under normal pressure, obtains Chinese red
The polyethers amido APG aqueous solution of clear viscous, water removal obtains final product polyethers amido APG product；
Described epoxides be oxirane, expoxy propane in one or two；
Described APG is the one kind in methylglycoside, ethyl glucoside, propyl glucoside, butyl glycoside；
Described organic amine is the one kind in ethylenediamine, diethylenetriamine, triethylene tetramine, TEPA.
3. the drilling fluid as claimed in claim 2 preparation method of polyethers amido APG, it is characterised in that described urges
Agent is the mixture of the compounding of inorganic acid, organic acid or inorganic acid and organic acid.
4. the drilling fluid as claimed in claim 3 preparation method of polyethers amido APG, it is characterised in that described nothing
Machine acid is the one kind in sulfuric acid, nitric acid, phosphoric acid, phosphotungstic acid.
5. the drilling fluid as claimed in claim 3 preparation method of polyethers amido APG, it is characterised in that described has
Machine acid is the one kind in p-methyl benzenesulfonic acid, DBSA, sulfamic acid.
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Families Citing this family (16)
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| CN106350039A (en) * | 2015-07-17 | 2017-01-25 | 中石化石油工程技术服务有限公司 | Polyether amine-based alkyl glycoside oil-based drilling fluid and preparation method thereof |
| CN106701046A (en) * | 2015-07-17 | 2017-05-24 | 中石化石油工程技术服务有限公司 | Soilless polyether amine alkyl glucoside drilling fluid and preparation method thereof |
| CN106432376B (en) * | 2015-08-10 | 2019-02-22 | 中石化石油工程技术服务有限公司 | A kind of aminoalkyl glucosides and its preparation method and application |
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| CN106432375B (en) * | 2015-08-10 | 2019-02-22 | 中石化石油工程技术服务有限公司 | A kind of polyethers amido alkyl glycosides and its preparation method and application |
| CN106432378B (en) * | 2015-08-10 | 2020-04-24 | 中石化石油工程技术服务有限公司 | Polyaminoalkyl glucoside and preparation method and application thereof |
| CN106467725B (en) * | 2015-08-14 | 2019-04-12 | 中石化石油工程技术服务有限公司 | A kind of biomass drilling base liquid, preparation method and its application |
| CN105838342A (en) * | 2016-04-24 | 2016-08-10 | 辽宁石油化工大学 | High-density cationic saccharide inhibitor for drilling fluids and preparation method thereof |
| CN107973827A (en) * | 2016-10-25 | 2018-05-01 | 中石化石油工程技术服务有限公司 | A kind of aminoalkyl glucosides graft copolymer and preparation method thereof and drilling fluid |
| CN107987808A (en) * | 2016-10-26 | 2018-05-04 | 中石化石油工程技术服务有限公司 | A kind of drilling fluid |
| CN109694699A (en) * | 2017-10-23 | 2019-04-30 | 中石化石油工程技术服务有限公司 | A kind of shale oil air water horizontal well water-base drilling fluid |
| CN109957384B (en) * | 2017-12-14 | 2021-06-15 | 中国石油化工股份有限公司 | Cation-nonionic alcohol ether glucoside type drag reducer |
| CN108148103B (en) * | 2017-12-30 | 2021-02-09 | 江南大学 | Synthesis process of alkyl polyglycoside hydroxypropyl sodium sulfonate |
| CN111320659B (en) * | 2018-12-13 | 2022-12-13 | 中石化石油工程技术服务有限公司 | Sulfamidoglyceryl glycoside, preparation method thereof and drilling fluid |
| CN111320661A (en) * | 2018-12-13 | 2020-06-23 | 中石化石油工程技术服务有限公司 | Polyamino sulfonated alkyl glycoside, preparation method thereof and drilling fluid |
| CN110947338B (en) * | 2019-12-09 | 2021-10-12 | 南京科技职业学院 | Alkyl glycoside sulfobetaine type amphoteric surfactant and preparation method thereof |
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Effective date of registration: 20180723 Address after: 100029 Chaoyangmen North Street, Chaoyang District, Chaoyang District, Beijing Co-patentee after: Drilling Research Institute of Zhongyuan Petroleum Engineering Co., Ltd. Sinopec Patentee after: Sinopec Corp. Co-patentee after: SINOPEC OILFIELD SERVICE CORPORATION Co-patentee after: SINOPEC ZHONGYUAN PETROLEUM ENGINEERING CO., LTD. Address before: 100728 Chaoyangmen North Street, Chaoyang District, Chaoyang District, Beijing Co-patentee before: Drilling Research Institute of Zhongyuan Petroleum Engineering Co., Ltd. Sinopec Patentee before: Sinopec Corp. |