CN104592956A - High-efficiency polyamine shale inhibitor preparation method - Google Patents
High-efficiency polyamine shale inhibitor preparation method Download PDFInfo
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- CN104592956A CN104592956A CN201310530809.0A CN201310530809A CN104592956A CN 104592956 A CN104592956 A CN 104592956A CN 201310530809 A CN201310530809 A CN 201310530809A CN 104592956 A CN104592956 A CN 104592956A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/024—Polyamines containing oxygen in the form of ether bonds in the main chain
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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
- C09K8/035—Organic additives
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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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Abstract
The invention discloses a preparation method of a high-efficiency polyamine shale inhibitor. The method comprises the following steps: (1) cyclic ether is added into straight-chain amine under stirring and under a temperature of 50-90 DEG C, wherein a molar ratio of the straight-chain amine to the added cyclic ether is 1:2-3, and a reaction time is 1-4h; (2) the temperature of the material obtained in the step (1) is increased to 70-110 DEG C; epichlorohydrin is added under stirring, wherein the molar ratio of epichlorohydrin to the straight-chain amine is 0.4-0.9:1; and (3) water is added into the material obtained in the step (2), wherein the molecular ratio of water to the straight-chain amine is 1-2:1; a reaction is allowed for 1-2h, and the polyamine shale inhibitor is obtained after the reaction. With the method, the prepared polyamine shale inhibitor has excellent shale inhibition performance even under a low content. The synthesis method is simple; cost is low; no special odor is caused; and the method is environment-friendly.
Description
Technical field
The present invention relates to a kind of efficient polyamine shale control agent and preparation method thereof.
Background technology
Drilling fluid refers in oil/gas drilling process, meets the general name of the various circulating fluid of drilling well demand with its several functions.The function of drilling fluid mainly contains: carry and suspend drilling cuttings; Stabilizing borehole and equilibrium strata pressure; Cooling and Lubricator drill bit, drilling tool; Transmit water power.
Along with the development of petroleum exploration domain, deep-well, ultra deep well, the appearance of ocean well and complex ground well, drilling well difficulty increases, also more and more strict to the requirement of drilling fluid system.Particularly in oil gas drilling process, when boring chance mud shale stratum, hydration swelling, the dispersion of mud shale will cause the series of problems such as borehole well instability, bit balling and hole cleaning.Traditional oil base drilling fluid, possesses many good performances, but its contaminate environment, application is restricted.The high performance water-based drilling fluid being main shale control agent with polyamine class becomes with its environmental protection, low cost, the characteristic such as functional the study hotspot that countries in the world oil investigator pays close attention to.
Polyamine base polymer is as main shale inhibitor, its mechanism of action is: worked by the distinctive absorption of amido, low molecule amine penetrates clay layer as potassium ion, the exchangeable cation of the subsidiary hydration shell of amine desorb of lower concentration, together with by electrostatic adhesion, hydrogen bond action and dipole effect etc. clay lamella being strapped in, stop water molecules to enter, play the effect that shale suppresses.
Polyamine class shale control agent is mainly based on macrocation, small cation.Macrocation is polyamine methacryloyl amine quaternary ammonium salt, as suppressed dose of clay bag; Small cation is epoxypropyltrimethylchloride chloride.Small cation molecular weight is little, with positive charge, is easily adsorbed in surface of clay, and enters between clay seam, replaces exchangeable cation and is adsorbed in wherein.And the surface at its binding molecule place is the hydrophobic surface containing hydrocarbon group, is conducive to stoping water molecules to enter, therefore effectively can suppresses hydration swelling and the dispersion of clay.
Polyether monoamine inhibitor is the ULTRADRIL that MISWACO company of the U.S. releases in recent years
tMhighly inhibited water-base drilling fluid.It is the people such as Patel develop be not hydrolyzed, completely water-soluble, low toxicity and with other conventional water-based drilling solution additive compatibility, its shale inhibition can be better than size cationic polymers.
All kinds of performance of drilling fluid that it is shale control agent that Chinese patent CN 1069755A describes with large small cation, size cationic drilling fluid system shale inhibition can be better.US Patent No. 7012043 B2 describes polyether monoamine inhibitor, and such inhibitor shows good mud shale rejection ability.Macrocation backbone structure or be connected with C-C key between side chain with main chain, branched fraction contains C-N key; Small cation is containing C-C, C-N ,-O-key.Polyether monoamine inhibitor based on C-C ,-O-, in chain or the end of the chain contain a small amount of C-N key.The result that the basic reason of the strong rejection capability of polyether monoamine is in its main chain or a small amount of multiple amido of the end of the chain acts on simultaneously, therefore ability of its constraint hydration and expansion of clay is stronger, shows strong rejection capability.CN201110313847.1 describes a kind of preparation method of cationic polyamine shale control agent, to hold diamines, cyclic ethers, epoxy chloropropane for raw material, obtained after polymerization.This shale control agent inhibition when high density is given prominence to, but the inhibition when lower concentration needs to improve further.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of preparation method of efficient polyamine class shale control agent.Polyamine class shale control agent prepared by the method also has superior mud shale rejection when low levels, and synthetic method is simple, and cost is low, without special odor, environmental friendliness.
A preparation method for efficient polyamine class shale control agent, comprises following content:
(1) under stirring and 50 ~ 90 DEG C of conditions, add cyclic ethers in straight chain amine, straight chain amine and the cyclic ethers mol ratio added are 1:2 ~ 3, and the reaction times is 1 ~ 4h; Preferable reaction temperature is 65 ~ 75 DEG C, and the cyclic ethers mol ratio of straight chain amine and dropping is 1:2 ~ 2.5, and the reaction times is 2 ~ 3 h;
(2) step (1) temperature of charge is risen to 70 ~ 110 DEG C, preferably 85 ~ 100 DEG C, under agitation condition, add epoxy chloropropane, the mol ratio of epoxy chloropropane and straight chain amine is 0.4 ~ 0.9:1, preferably 0.5 ~ 0.8:1, the reaction times is 1 ~ 3h, preferably 1.5 ~ 2h;
(3) add water in the material of step (2), the mol ratio of water and straight chain amine is 1 ~ 2:1, preferably 1 ~ 1.8:1, and the reaction times is 1 ~ 2h, preferably 1 ~ 1.5h, obtained polyamine class shale control agent after reaction.
In the inventive method, described straight chain amine can be polyethylene polyamine or end diamines, preferred polyethylene polyamine.Employing polyethylene polyamine can improve rejection during low levels further; In addition, chain have polyethylene polyamine and the end diamines of same atoms number, the reactive behavior of polyethylene polyamine will apparently higher than end diamines, this makes the present invention can carry out under lower temperature of reaction, at the same reaction temperature, reaction times obviously shortens, and effectively reduces operational danger and synthesis cost.
In the inventive method, polyethylene polyamine can be diethylenetriamine, triethylene tetramine, tetraethylene pentamine, five ethene hexamines etc.; End diamines can be quadrol, propylene diamine, butanediamine, pentamethylene diamine, hexanediamine etc.Described cyclic ethers is oxyethane, propylene oxide etc.Described water is deionized water.
The inventive method uses deionized water to replace conventional sour terminator, and stop polyreaction by the hydrolytic action of polymer-based group, the shale control agent prepared, while having good rejection, significantly improves compatibleness.
Embodiment
Illustrate the effect of the inventive method below in conjunction with embodiment, but following examples do not form the restriction to the present invention program.
Embodiment 1
First temperature of reaction is set as 65 DEG C, stir and pass in diethylenetriamine by oxyethane, the mol ratio of diethylenetriamine and oxyethane is 1:2, controls temperature of reaction and is not less than 60 DEG C, reaction 3h; Then temperature is risen to 80 DEG C, drip epoxy chloropropane under agitation condition, the mol ratio of epoxy chloropropane and diethylenetriamine is 0.6:1, reaction times is 1.5h, finally add water, the mol ratio of water and diethylenetriamine is 1:1, obtained polyamine class shale control agent after reaction 1h.
Embodiment 2
Temperature of reaction is set as 75 DEG C, stir and be added drop-wise in triethylene tetramine by propylene oxide, the mol ratio of triethylene tetramine and propylene oxide is 1:3, controls temperature of reaction and is not less than 70 DEG C, reaction 2h; Then temperature is risen to 90 DEG C, drip epoxy chloropropane under agitation condition, the mol ratio of rubbing of epoxy chloropropane and diethylenetriamine is 0.5:1, and the reaction times is 1h; Finally add water, the mol ratio of water and diethylenetriamine is 1.5:1, obtained polyamine class shale control agent after reaction 1h.
Embodiment 3
Temperature of reaction is set as 85 DEG C, stir and be added drop-wise in tetraethylene pentamine by propylene oxide, the mol ratio of tetraethylene pentamine and propylene oxide is 1:2.5, controls temperature of reaction and is not less than 80 DEG C, reaction 1.5h; Then temperature is risen to 100 DEG C, drip epoxy chloropropane under agitation condition, the mol ratio of rubbing of epoxy chloropropane and diethylenetriamine is 0.8:1, and the reaction times is 1.5h; Finally add water, the mol ratio of water and diethylenetriamine is 1.8:1, obtained polyamine class shale control agent after reaction 1h.
Embodiment 4
With embodiment 1, just raw material diethylenetriamine becomes hexanediamine.
Embodiment 5
With embodiment 2, just raw material triethylene tetramine becomes propylene diamine.
Comparative example 1
Just finally add hydrochloric acid with embodiment 1 and replace water.
Comparative example 2
Just finally add hydrochloric acid with embodiment 4 and replace water.
The evaluation method of above-described embodiment and the polyamine inhibitor involved by comparative example is as follows:
Get 350 ml distilled waters, add 1.05g(and be accurate to 0.01g) sodium carbonate, stir 5min under 10000r/min after, slowly add 35g(and be accurate to 0.01g) drilling fluid wilkinite, 20min is stirred under 10000r/min, 120 DEG C time, heat rolls 16h, stirs 5min after cooling under 10000 ± 300r/min, measures the value of base slurry at 24 ± 3 DEG C.
The sample getting certain mass is dissolved in 350 ml distilled waters, stir, add 1.05g(again and be accurate to 0.01g) sodium carbonate, stir 5min under 10000r/min after, slowly add 35g(and be accurate to 0.01g) drilling fluid wilkinite, under 10000r/min, stir 20min, 120 DEG C time, heat rolls 16h, under 10000 ± 300r/min, stir 5min after cooling, at 24 ± 3 DEG C, location survey determines the value of mud.
Different polyamine contrast test result is as follows: following % is mass percentage
The relative inhibition of the different polyamine inhibitor of table 1
Experiment condition: 120 DEG C of heat roll 16h, wilkinite mass concentration 10%.
Claims (10)
1. a preparation method for efficient polyamine class shale control agent, is characterized in that: comprise following content:
(1) under stirring and 50 ~ 90 DEG C of conditions, add cyclic ethers in straight chain amine, straight chain amine and the cyclic ethers mol ratio added are 1:2 ~ 3, and the reaction times is 1 ~ 4h;
(2) step (1) temperature of charge is risen to 70 ~ 110 DEG C, add epoxy chloropropane under agitation condition, the mol ratio of epoxy chloropropane and straight chain amine is 0.4 ~ 0.9:1, and the reaction times is 1 ~ 3h;
(3) add water in the material of step (2), the mol ratio of water and straight chain amine is 1 ~ 2:1, and the reaction times is 1 ~ 2h, obtained polyamine class shale control agent after reaction.
2. method according to claim 1, is characterized in that: in step (1), temperature of reaction is 65 ~ 75 DEG C, and the cyclic ethers mol ratio of straight chain amine and dropping is 1:2 ~ 2.5, and the reaction times is 2 ~ 3 h.
3. method according to claim 1, is characterized in that: the straight chain amine described in step (1) is polyethylene polyamine or end diamines.
4. method according to claim 1, is characterized in that: described straight chain amine is polyethylene polyamine.
5. the method according to claim 3 or 4, is characterized in that: polyethylene polyamine is one or more in diethylenetriamine, triethylene tetramine, tetraethylene pentamine, five ethene hexamines.
6. method according to claim 3, is characterized in that: end diamines is one or more in quadrol, propylene diamine, butanediamine, pentamethylene diamine, hexanediamine.
7. method according to claim 1, is characterized in that: the cyclic ethers described in step (1) is oxyethane, propylene oxide.
8. method according to claim 1, is characterized in that: temperature of charge 85 ~ 100 DEG C in step (2), the mol ratio of epoxy chloropropane and straight chain amine is 0.5 ~ 0.8:1, and the reaction times is 1.5 ~ 2h.
9. method according to claim 1, is characterized in that: in step (3), the mol ratio of water and straight chain amine is 1 ~ 1.8:1, and the reaction times is 1 ~ 1.5h.
10. method according to claim 1, is characterized in that: the water described in step (3) is deionized water.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104927051A (en) * | 2015-06-17 | 2015-09-23 | 西南石油大学 | Nanometer polymer blocking agent for water-based drilling fluid and preparation method thereof |
| CN105038738A (en) * | 2015-07-14 | 2015-11-11 | 中国石油天然气集团公司 | High-temperature resistant efficient mud shale inhibitor for drilling fluid and preparation method therefor |
| CN106350036A (en) * | 2016-08-22 | 2017-01-25 | 西南石油大学 | Alkyl tetramine synthesis method, alkyl tetramine product and shale inhibitor thereof |
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| EP2062957A1 (en) * | 2007-11-21 | 2009-05-27 | Lamberti Spa | Swelling inhibitors for clays and shales |
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2013
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Patent Citations (4)
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| US4029708A (en) * | 1975-02-10 | 1977-06-14 | Nalco Chemical Company | Linear surfactant polymers formed from substituted amines and difunctional reactants |
| EP2062957A1 (en) * | 2007-11-21 | 2009-05-27 | Lamberti Spa | Swelling inhibitors for clays and shales |
| CN101717624A (en) * | 2009-11-17 | 2010-06-02 | 中国海洋石油总公司 | High-efficient water-based well drilling fluid with fast absorption, strong inhibition and low damage |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104927051A (en) * | 2015-06-17 | 2015-09-23 | 西南石油大学 | Nanometer polymer blocking agent for water-based drilling fluid and preparation method thereof |
| CN104927051B (en) * | 2015-06-17 | 2017-02-22 | 西南石油大学 | Nanometer polymer blocking agent for water-based drilling fluid and preparation method thereof |
| CN105038738A (en) * | 2015-07-14 | 2015-11-11 | 中国石油天然气集团公司 | High-temperature resistant efficient mud shale inhibitor for drilling fluid and preparation method therefor |
| CN106350036A (en) * | 2016-08-22 | 2017-01-25 | 西南石油大学 | Alkyl tetramine synthesis method, alkyl tetramine product and shale inhibitor thereof |
| CN106350036B (en) * | 2016-08-22 | 2018-11-06 | 西南石油大学 | A kind of synthetic method of alkyl tetramine, four amine product of alkyl and its shale control agent |
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Effective date of registration: 20230824 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |