CN103666412A - Compound amine shale inhibitor - Google Patents

Compound amine shale inhibitor Download PDF

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Publication number
CN103666412A
CN103666412A CN201210333239.1A CN201210333239A CN103666412A CN 103666412 A CN103666412 A CN 103666412A CN 201210333239 A CN201210333239 A CN 201210333239A CN 103666412 A CN103666412 A CN 103666412A
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Prior art keywords
ammonium
aliphatics
group
amine
several
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Inventor
江瑞晶
戴杰
袁俊秀
王康
黄冬
杨智中
金钢
逯贵广
朱魁
徐冬梅
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China Petroleum and Chemical Corp
Research Institute of Sinopec Nanjing Chemical Industry Co Ltd
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China Petroleum and Chemical Corp
Research Institute of Nanjing Chemical Industry Group Co Ltd
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Priority to CN201210333239.1A priority Critical patent/CN103666412A/en
Publication of CN103666412A publication Critical patent/CN103666412A/en
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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
    • C09K8/035—Organic additives
    • 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
    • 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
    • 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
    • C09K2208/34—Lubricant additives

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention provides a compound amine shale inhibitor for a water-based drilling fluid. The compound amine shale inhibitor is characterized by consisting of 20.0-80.0% of free amine, 5.0-60.0% of Amine (ammonium) salt, 0.5-30.0% of a performance accelerant, 0.5-80.0% of water or other additives, totaling 100%. The inhibitor provided by the invention has superstrong inhibition performance and can effectively inhibit clay swelling and hydrated dispersion. The drilling fluid system prepared by the compound amine shale inhibitor not only is remarkable in inhibition performance, but also has good lubricating performance. The shale inhibitor has a better improving effect on mud cakes in the using process, and is free from bubbles and good in compatibility with other common polymer processors in the drilling fluid.

Description

A kind of compound amine shale control agent
Technical field
The invention belongs to petrochemical complex drilling technique field, a kind of compound amine shale control agent of using for high pulping, high water-sensitive formation unstability stratigraphical drilling engineering is provided.
Background technology
From a long time ago, ammonium salt or aminated compounds are just used as the shale inhibitor of drilling fluid.Wherein structure is the most simply NH 4cl.But NH 4the use shortcoming of Cl is that temperature resistance is poor, and easily decomposites obnoxious flavour NH while using in being generally alkaline water-base drilling fluid 3, thereby seldom use at situ of drilling well.
Select quaternary ammonium salt as shale inhibitor, as tetramethyl ammonium chloride, the inhibition of quaternary ammonium salt is relevant to system pH, when pH value is lower, inhibition is better, and the compatibleness of quaternary ammonium compound and anionic treatment agent is poor, and its toxicity is large, is not suitable for marine drilling.
The problem that is subject to the restriction of pH value and has toxicity for overcoming quaternary ammonium compound inhibition, researchist has developed a kind of amphipathic amino acid inhibitor, this inhibitor is completely water-soluble, Heat stability is good, be not hydrolyzed, safety and environmental protection is good with the compatibleness of other treatment agent, but this compound can not anhydrating the clay of aquation, the inhibition in high solid system is undesirable.
The mid-90 in 20th century, Jones etc. have released the better alkyl diamine class of rejection inhibitor as hexanediamine, and such compound alkyl chain is poisonous in short-term, but not soluble in water during alkyl chain length, and rejection is undesirable.Subsequently, it is low that Brady etc. have developed a kind of this inhibitor cost of many ethanol two amine inhibitors, low toxicity, but it is not good enough to the rejection of mud shale.
Summary of the invention
The invention provides a kind of compound amine shale control agent, this inhibitor can be inserted between clay seam, effectively suppressing clay swelling and aquation disperses, the drilling fluid system being mixed with compound amine inhibitor, not only rejection is outstanding, and there is good lubricity, and in use procedure, mud cake tool is had a better role, non-foaming.
Object of the present invention is achieved through the following technical solutions:
1) compound amine shale control agent comprises unhindered amina, amine (ammonium) salt, performance promotor, this four kinds of components of auxiliary agent.Wherein unhindered amina account for compound amine inhibitor total mass 20.0～80.0%, amine (ammonium) salt accounts for 5.0～60.0% of compound amine inhibitor total mass, performance accelerator content account for compound amine inhibitor total mass 0.5～30.0%, auxiliary agent accounts for 0.5～70.0% of compound amine inhibitor total mass.The effective constituent wherein playing a role is unhindered amina, amine (ammonium) salt and performance promotor three class materials.
2) described unhindered amina is one or several the mixture in following a few class material:
A) mixture of one or several in thanomin, diethanolamine, trolamine and thionamic acid;
B) there is the mixture of one or several amine in following several general structure:
Figure BDA00002117233500011
R 1, R 2and R 3independently selectable side chain or the straight chain aliphatics C of comprising 2~ C 4group; M:0 ~ 45; N:0 ~ 45; R 4and R 5be identical or different and be hydrogen or the aliphatics organic group with 1 to 6 carbon atom.
Figure BDA00002117233500021
R 1, R 2independently selectable side chain or the straight chain aliphatics C of comprising 2~ C 4group; X:0 ~ 23; N:0 ~ 23; R 3and R 4be identical or different and be hydrogen or the aliphatics organic group with 1 to 6 carbon atom.
Figure BDA00002117233500022
R 1, R 2independently selectable side chain or the straight chain aliphatics C of comprising 2~ C 4group; M:0 ~ 20; N:0 ~ 20.
3) described amine (ammonium) salt is one or several the mixture in following several material:
A) mixture of one or several in ammonium chloride, ammonium sulfate, ammonium phosphate, ammonium pyrophosphate, ammonium metaphosphate, volatile salt, Ammonium bicarbonate food grade, ammonium oxalate, ammonium acetate, ammonium formiate, ammonium citrate, butyric acid ammonium;
B) there is the mixture of one or several amine salt in following several general structure:
Figure BDA00002117233500023
R 1, R 2and R 3independently selectable side chain or the straight chain aliphatics C of comprising 2~ C 4group; X:0 ~ 45; Y:0 ~ 45; R, R 4and R 5be identical or different and be hydrogen or the aliphatics organic group with 1 to 6 carbon atom.
Figure BDA00002117233500024
R 1, R 2independently selectable side chain or the straight chain aliphatics C of comprising 2~ C 4group; X:0 ~ 23; N:0 ~ 23; R, R 3and R 4be identical or different and be hydrogen or the aliphatics organic group with 1 to 6 carbon atom.
Figure BDA00002117233500025
R 1, R 2and R 3independently selectable side chain or the straight chain aliphatics C of comprising 2~ C 4group; X:0 ~ 45; Y:0 ~ 45; R 4and R 5be identical or different and be hydrogen or the aliphatics organic group with 1 to 6 carbon atom; X represents that mineral acid follows ion, is likely Cl -, Br -, I -, SO 4 2-, PO 4 3-.
R 1, R 2independently selectable side chain or the straight chain aliphatics C of comprising 2~ C 4group; X:0 ~ 23; N:0 ~ 23; R 3and R 4be identical or different and be hydrogen or the aliphatics organic group with 1 to 6 carbon atom; X represents that mineral acid follows ion, is likely Cl -, Br -, I -, SO 4 2-, PO 4 3-.
4) described performance promotor mainly has following several general structure, is one or several mixture wherein:
C nH 2n+1OH （8）
Cn H 2n+1for carbon chain length is various positive structure or the isoparaffin between 3 ~ 20.
Figure BDA00002117233500031
R 1, R 2independently selectable side chain or the straight chain aliphatics C of comprising 2~ C 4group; M:3 ~ 45; N:3 ~ 45.
Inhibitor of the present invention has superpower rejection, effectively suppressing clay swelling and aquation disperses, the drilling fluid system being mixed with compound amine inhibitor, not only rejection is outstanding, and there is good lubricity, in use procedure, mud cake tool is had a better role, non-foaming, good with other polymer treatment agent compatibility conventional in drilling fluid.
Embodiment
Below in conjunction with embodiment, technique of the present invention is described.
Embodiment 1
According to the formula of table 1, the different compound amine shale control agents that form of preparation.
Figure BDA00002117233500041
Figure BDA00002117233500051
Figure BDA00002117233500061
Embodiment 2
Get 350 ml distilled waters (or compound amine inhibitor solution of the various formulas compositions that in table 1, massfraction is 1.0%), add 1.05g(to be accurate to 0.01g) sodium carbonate, under 10000r/min, stir after 5min, slowly add 35g(to be accurate to 0.01g) drilling fluid wilkinite, under 10000r/min, stir 20min, in the time of 80 ℃, heat is rolled 16h, stir 5min after cooling under 10000 ± 300r/min, by measuring each system
Figure BDA00002117233500071
reading calculates the relative inhibition of solution.Relative inhibition (X) calculation formula:
Figure BDA00002117233500072
Relative inhibition test-results is in Table 2.
Table 2 different concns polyamine relative inhibition
As seen from the data in Table 2, the relative inhibition of 1.0% various compound amine solution reaches more than 90%, illustrates that compound amine inhibitor has stronger rejection.
Embodiment 3
Inhibition with the evaluating combined amine inhibitors of landwaste rolling recovery test.
Landwaste: high mausoleum 4 wells, 2750～3300m well section; Stratigraphic horizon: Sha Xi mausoleum, Qianfo Cliff and gravity well, before using, with 3% aqueous hydrogen peroxide solution, process.
Take 4-8 order landwaste 50.0(G 0) g, add in high temperature ageing still, subsequently various compound amine inhibitor solutions in the table 1 of massfraction 1.0% are added in aging still to scale marks place, 80 ℃ of heat are rolled after 16h, cross 100 orders (0.15mm) sieve, 105 ℃ of dry 4h of residues, are cooled to room temperature in moisture eliminator, weigh (G1), measure varies solution landwaste rolling rate of recovery R 1, R 1calculation formula:
Shale recovery ratio was a: R 1=G 1/ G 0* 100%(2)
Bits rolling recovery test the results are shown in Table 3.
The table 3 landwaste rolling rate of recovery
As seen from the data in Table 3, compound amine inhibitor has good rejection, and with respect to clear water, the 1.0% compound amine solution landwaste rolling rate of recovery can improve more than 25%.In table 2, table 3, inhibitor solution is as a comparison case inhibitor conventional on present market.

Claims (5)

1. a compound amine shale control agent, is characterized in that it comprises 20.0～80.0% unhindered aminas, 5.0～60.0% amine (ammonium) salt, 0.5～30.0% performance promotor, 0.5～70.0% auxiliary agent, and each component by percentage to the quality.
2. compound amine shale control agent according to claim 1, is characterized in that described auxiliary agent is one or more in water, sodium carbonate, Repone K, sodium-chlor, polyacrylic acid potassium, polyacrylamide, Polyanionic Cellulose.
3. compound amine shale control agent according to claim 1, is characterized in that described unhindered amina is one or several the mixture in following a few class material:
A) mixture of one or several in thanomin, diethanolamine, trolamine and thionamic acid;
B) there is the mixture of one or several amine in following several general structure:
Figure FDA00002117233400011
R 1, R 2and R 3independently selectable side chain or the straight chain aliphatics C of comprising 2~ C 4group; M:0 ~ 45; N:0 ~ 45; R 4and R 5be identical or different and be hydrogen or the aliphatics organic group with 1 to 6 carbon atom.
Figure FDA00002117233400012
R 1, R 2independently selectable side chain or the straight chain aliphatics C of comprising 2~ C 4group; X:0 ~ 23; N:0 ~ 23; R 3and R 4be identical or different and be hydrogen or the aliphatics organic group with 1 to 6 carbon atom.
Figure FDA00002117233400013
R 1, R 2independently selectable side chain or the straight chain aliphatics C of comprising 2~ C 4group; M:0 ~ 20; N:0 ~ 20.
4. compound amine shale control agent according to claim 1, is characterized in that described amine (ammonium) salt is one or several the mixture in following several material:
A) mixture of one or several in ammonium chloride, ammonium sulfate, ammonium phosphate, ammonium pyrophosphate, ammonium metaphosphate, volatile salt, Ammonium bicarbonate food grade, ammonium oxalate, ammonium acetate, ammonium formiate, ammonium citrate, butyric acid ammonium;
B) there is the mixture of one or several amine salt in following several general structure:
R 1, R 2and R 3independently selectable side chain or the straight chain aliphatics C of comprising 2~ C 4group; X:0 ~ 45; Y:0 ~ 45; R, R 4and R 5be identical or different and be hydrogen or the aliphatics organic group with 1 to 6 carbon atom;
Figure FDA00002117233400021
R 1, R 2independently selectable side chain or the straight chain aliphatics C of comprising 2~ C 4group; X:0 ~ 23; N:0 ~ 23; R, R 3and R 4be identical or different and be hydrogen or the aliphatics organic group with 1 to 6 carbon atom;
Figure FDA00002117233400022
R 1, R 2and R 3independently selectable side chain or the straight chain aliphatics C of comprising 2~ C 4group; X:0 ~ 45; Y:0 ~ 45; R 4and R 5be identical or different and be hydrogen or the aliphatics organic group with 1 to 6 carbon atom; X represents that mineral acid follows ion, is likely Cl -, Br -, I -, SO 4 2-, PO 4 3-;
Figure FDA00002117233400023
R 1, R 2independently selectable side chain or the straight chain aliphatics C of comprising 2~ C 4group; X:0 ~ 23; N:0 ~ 23; R 3and R 4be identical or different and be hydrogen or the aliphatics organic group with 1 to 6 carbon atom; X represents that mineral acid follows ion, is likely Cl -, Br -, I -, SO 4 2-, PO 4 3-.
5. compound amine shale control agent according to claim 1, is characterized in that described performance promotor has following several general structure, is one or several mixture wherein:
C nH 2n+1OH
（8）
C nh 2n+1for carbon chain length is various positive structure or the isoparaffin between 3 ~ 20;
Figure FDA00002117233400024
R 1, R 2independently selectable side chain or the straight chain aliphatics C of comprising 2~ C 4group; M:3 ~ 45; N:3 ~ 45.
CN201210333239.1A 2012-09-10 2012-09-10 Compound amine shale inhibitor Pending CN103666412A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104449599A (en) * 2014-10-30 2015-03-25 中国石油化工股份有限公司 Anti-swelling agent for clay
CN105505341A (en) * 2014-09-23 2016-04-20 中国石油化工股份有限公司 Clay anti-swelling agent
CN105623636A (en) * 2014-10-27 2016-06-01 中国石油天然气股份有限公司 Anti-swelling and anti-shrinking agent, preparation method and application thereof
CN105670574A (en) * 2014-11-21 2016-06-15 中石化胜利石油工程有限公司钻井工艺研究院 Drilling fluid ether-amine compound inhibitor and preparation method thereof
CN106281263A (en) * 2016-08-08 2017-01-04 西南石油大学 A kind of Ultra-low molecular weight intercalation inhibitor and preparation method thereof
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
CN115838590A (en) * 2021-09-18 2023-03-24 中国石油化工股份有限公司 Low-cost high-efficiency anti-swelling agent for fracturing and preparation method and use method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101864283A (en) * 2009-12-11 2010-10-20 中国石油集团钻井工程技术研究院 Water-based drilling fluid composition containing amine compound
CN102250595A (en) * 2011-05-19 2011-11-23 中国石油天然气集团公司 Drilling fluid used for active mud shale drilling

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101864283A (en) * 2009-12-11 2010-10-20 中国石油集团钻井工程技术研究院 Water-based drilling fluid composition containing amine compound
CN102250595A (en) * 2011-05-19 2011-11-23 中国石油天然气集团公司 Drilling fluid used for active mud shale drilling

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105505341A (en) * 2014-09-23 2016-04-20 中国石油化工股份有限公司 Clay anti-swelling agent
CN105505341B (en) * 2014-09-23 2018-05-01 中国石油化工股份有限公司 A kind of anti-clayswelling agent
CN105623636A (en) * 2014-10-27 2016-06-01 中国石油天然气股份有限公司 Anti-swelling and anti-shrinking agent, preparation method and application thereof
CN105623636B (en) * 2014-10-27 2019-05-07 中国石油天然气股份有限公司 Anti-swelling and anti-shrinking agent, preparation method and application thereof
CN104449599A (en) * 2014-10-30 2015-03-25 中国石油化工股份有限公司 Anti-swelling agent for clay
CN105670574A (en) * 2014-11-21 2016-06-15 中石化胜利石油工程有限公司钻井工艺研究院 Drilling fluid ether-amine compound inhibitor and preparation method thereof
CN106281263A (en) * 2016-08-08 2017-01-04 西南石油大学 A kind of Ultra-low molecular weight intercalation inhibitor and preparation method thereof
CN106281263B (en) * 2016-08-08 2018-11-09 西南石油大学 A kind of Ultra-low molecular weight intercalation inhibitor and preparation method thereof
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
CN115838590A (en) * 2021-09-18 2023-03-24 中国石油化工股份有限公司 Low-cost high-efficiency anti-swelling agent for fracturing and preparation method and use method thereof

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Application publication date: 20140326