CN113527131B - Polyamine with inhibition and solid phase cleaning functions, and preparation method and application thereof - Google Patents
Polyamine with inhibition and solid phase cleaning functions, and preparation method and application thereof Download PDFInfo
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- CN113527131B CN113527131B CN202011597042.XA CN202011597042A CN113527131B CN 113527131 B CN113527131 B CN 113527131B CN 202011597042 A CN202011597042 A CN 202011597042A CN 113527131 B CN113527131 B CN 113527131B
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- 229920000768 polyamine Polymers 0.000 title claims abstract description 91
- 238000004140 cleaning Methods 0.000 title claims abstract description 60
- 239000007790 solid phase Substances 0.000 title claims abstract description 58
- 230000005764 inhibitory process Effects 0.000 title claims description 40
- 238000002360 preparation method Methods 0.000 title claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 230000000694 effects Effects 0.000 claims abstract description 24
- 238000005553 drilling Methods 0.000 claims abstract description 21
- 239000012530 fluid Substances 0.000 claims abstract description 20
- 230000002401 inhibitory effect Effects 0.000 claims abstract description 20
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 6
- 239000013067 intermediate product Substances 0.000 claims description 48
- 238000010438 heat treatment Methods 0.000 claims description 47
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 42
- 150000002924 oxiranes Chemical class 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 34
- 239000004698 Polyethylene Substances 0.000 claims description 28
- -1 polyethylene Polymers 0.000 claims description 28
- 229920000573 polyethylene Polymers 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 16
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 16
- 230000035484 reaction time Effects 0.000 claims description 15
- 239000003377 acid catalyst Chemical class 0.000 claims description 14
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical group ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 8
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical group CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 7
- 150000003944 halohydrins Chemical class 0.000 claims description 6
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 4
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims description 4
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 abstract description 5
- 239000003112 inhibitor Substances 0.000 abstract description 5
- 230000036571 hydration Effects 0.000 abstract description 3
- 238000006703 hydration reaction Methods 0.000 abstract description 3
- 238000004537 pulping Methods 0.000 abstract description 3
- 239000002002 slurry Substances 0.000 description 17
- 239000002689 soil Substances 0.000 description 15
- 239000011435 rock Substances 0.000 description 12
- 238000011084 recovery Methods 0.000 description 11
- 239000012634 fragment Substances 0.000 description 9
- 238000001816 cooling Methods 0.000 description 7
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 229910000281 calcium bentonite Inorganic materials 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 125000006833 (C1-C5) alkylene group Chemical group 0.000 description 1
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/34—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups
- C07C233/35—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
- C07C233/36—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom having the carbon atom of the carboxamide group bound to a hydrogen atom or to a carbon atom of an acyclic saturated carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
- C07C209/08—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/10—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes
- C07C29/103—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes of cyclic ethers
- C07C29/106—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes of cyclic ethers of oxiranes
-
- 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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- 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
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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
- C09K8/04—Aqueous well-drilling compositions
- C09K8/14—Clay-containing compositions
- C09K8/18—Clay-containing compositions characterised by the organic compounds
- C09K8/22—Synthetic organic compounds
- C09K8/24—Polymers
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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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- Dispersion Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention provides polyamine with inhibiting and solid phase cleaning effects, which has a structure shown in a formula (I); wherein m is an integer of 1 to 10, n is an integer of 1 to 5, and R is a C1 to C5 alkylene group. Compared with the prior art, the polyamine provided by the invention has a better inhibitor solid phase cleaning effect under a high temperature condition, and also has better compatibility in drilling fluid, and when the polyamine is applied to the drilling fluid, the polyamine can not only effectively solve the problem of well wall instability of a strong water-sensitive shale stratum, but also effectively avoid the problem of well wall pulping of the drilling fluid caused by hydration of drill cuttings, and ensure well wall stability and well wall cleaning of the drilling fluid.
Description
Technical Field
The invention belongs to the technical field of oilfield chemical drilling fluid treatment agents, and particularly relates to polyamine with inhibition and solid phase cleaning functions, a preparation method and application thereof.
Background
Along with the continuous expansion of the oil and gas exploration and development range, deep wells, ultra-deep wells, high-inclination directional wells and long-section horizontal wells are more and more, high-temperature high-activity shale, mudstone interbedded and other complex strata are more and more drilled, and the difficulty of well wall stabilization is also more and more increased. The existing inhibitor can better solve the problem of instability of the well wall of the high-activity shale stratum, but has a well wall stabilizing effect on the stratum which is easy to collapse by the high-temperature high-activity shale and still needs to be improved in the solid phase cleaning effect of the high-temperature drilling fluid. Therefore, the development of high-temperature resistant shale strong inhibitor and drilling fluid solid phase cleaner is imperative, meets the urgent need of the drilling site technology, and has great significance.
Disclosure of Invention
In view of the above, the present invention provides a polyamine having both inhibition and solid phase cleaning effects, a preparation method and application thereof.
The invention provides a polyamine with inhibition and solid phase cleaning functions, which has a structure shown in a formula (I):
wherein m is an integer of 1 to 10, n is an integer of 1 to 5, and R is a C1 to C5 alkylene group.
Preferably, n is 3; the R is CH 2 Or C 2 H 4 。
The invention also provides a preparation method of the polyamine with both inhibition and solid phase cleaning effects, which comprises the following steps:
s1) mixing halogenated epoxide, water and an acid catalyst, heating and reacting to obtain halogenated alcohol solution;
s2) mixing the halohydrin solution with polyethylene polyamine, heating and reacting to obtain an intermediate product I;
s3) mixing the intermediate product I with dihaloethane, heating and reacting to obtain an intermediate product II;
s4) mixing the intermediate product II with polyethylene polyamine, heating and reacting to obtain an intermediate product III;
s5) adding acetic acid into the intermediate product III, and heating to generate a chain termination reaction to obtain the polyamine with the functions of inhibiting and cleaning a solid phase.
Preferably, the halogenated epoxide is selected from the group consisting of C3 to C7 chloroepoxides; the acid catalyst is selected from one or more of concentrated sulfuric acid, concentrated hydrochloric acid, p-toluenesulfonic acid and dodecylbenzenesulfonic acid; the polyethylene polyamine is selected from one or more of diethylenetriamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine; the dihaloethane is selected from dichloroethane.
Preferably, the halogenated epoxide is selected from epichlorohydrin and/or epichlorohydrin; the polyethylene polyamine is selected from tetraethylenepentamine.
Preferably, the mass ratio of the halogenated epoxide, water and the acid catalyst is 38: (60-120): (4-8); the mass ratio of the polyethylene polyamine to the halogenated epoxide in the step S2) is (70-90): 38, a step of carrying out the process; the mass ratio of the dihaloethane to the halogenated epoxide is (40-60): 38, a step of carrying out the process; the mass ratio of polyethylene polyamine to halogenated epoxide in the step S4) is (140-200): 38, a step of carrying out the process; the mass ratio of the acetic acid to the halogenated epoxide is (50-70): 38.
preferably, the temperature of the heating reaction in the step S1) is 85-95 ℃; the heating reaction time is 0.5-1 h;
the temperature of the heating reaction in the step S2) is 60-90 ℃; the heating reaction time is 1-2 h;
the temperature of the heating reaction in the step S3) is 80-105 ℃; the heating reaction time is 2-4 h;
the temperature of the heating reaction in the step S4) is 70-95 ℃; the heating reaction time is 2-4 h;
the temperature of the chain termination reaction in the step S5) is 50-70 ℃; the heating reaction time is 0.5-1 h.
Preferably, the reactions in steps S1) to S5) are all carried out under stirring; the stirring speed is preferably 500-1000 r/min.
The invention also provides a drilling fluid which comprises the polyamine with the inhibition and solid phase cleaning functions.
The invention provides polyamine with inhibiting and solid phase cleaning effects, which has a structure shown in a formula (I); wherein m is an integer of 1 to 10, n is an integer of 1 to 5, and R is a C1 to C5 alkylene group. Compared with the prior art, the polyamine provided by the invention has a better inhibitor solid phase cleaning effect under a high temperature condition, and also has better compatibility in drilling fluid, and when the polyamine is applied to the drilling fluid, the polyamine can not only effectively solve the problem of well wall instability of a strong water-sensitive shale stratum, but also effectively avoid the problem of well wall pulping of the drilling fluid caused by hydration of drill cuttings, and ensure well wall stability and well wall cleaning of the drilling fluid.
Drawings
FIG. 1 is an infrared spectrum of a polyamine having both inhibition and solid phase cleaning functions obtained in example 1 of the present invention.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a polyamine with inhibition and solid phase cleaning functions, which has a structure shown in a formula (I):
wherein m is an integer of 1 to 10, n is an integer of 1 to 5, preferably an integer of 2 to 4, more preferably 3; r is a C1-C5 alkylene group, preferablyIs a C1-C4 alkylene group, more preferably a C1-C3 alkylene group, still more preferably CH 2 Or C 2 H 4 。
The polyamine provided by the invention has a good inhibitor solid phase cleaning effect under a high temperature condition, and also has good compatibility in drilling fluid, and when the polyamine is applied to the drilling fluid, the polyamine can not only effectively solve the problem of well wall instability of a strong water-sensitive shale stratum, but also effectively avoid the problem of well wall pulping caused by hydration of drill cuttings, and ensure well wall stability and well wall cleaning.
The invention also provides a preparation method of the polyamine with the inhibition and solid phase cleaning functions, which comprises the following steps: s1) mixing halogenated epoxide, water and an acid catalyst, heating and reacting to obtain halogenated alcohol solution; s2) mixing the halohydrin solution with polyethylene polyamine, heating and reacting to obtain an intermediate product I; s3) mixing the intermediate product I with dihaloethane, heating and reacting to obtain an intermediate product II; s4) mixing the intermediate product II with polyethylene polyamine, heating and reacting to obtain an intermediate product III; s5) adding acetic acid into the intermediate product III, and heating to generate a chain termination reaction to obtain the polyamine with the functions of inhibiting and cleaning a solid phase.
The source of all the raw materials is not particularly limited, and the raw materials are commercially available.
Mixing halogenated epoxide, water and an acid catalyst, heating and reacting to obtain halogenated alcohol solution; the halogenated epoxide is preferably C3-C7 chloroepoxide, more preferably C3-C5 chloroepoxide, and still more preferably epichlorohydrin and/or epichlorohydrin; the acid catalyst is preferably one or more of concentrated sulfuric acid, concentrated hydrochloric acid, p-toluenesulfonic acid and dodecylbenzenesulfonic acid; the mass ratio of the halogenated epoxide, water and the acid catalyst is preferably 38: (60-120): (4-8); in some embodiments provided herein, the mass ratio of halogenated epoxide, water to acid catalyst is preferably 38:60:4, a step of; in some embodiments provided herein, the mass ratio of halogenated epoxide, water to acid catalyst is preferably 38:80:5, a step of; in some embodiments provided herein, the mass ratio of halogenated epoxide, water to acid catalyst is preferably 38:100:7, preparing a base material; in other embodiments provided by the present invention, the mass ratio of halogenated epoxide, water to acid catalyst is preferably 38:120:8, 8; the temperature of the heating reaction is preferably 85-95 ℃; the heating reaction time is preferably 0.5 to 1 hour; in the present invention, the reaction is preferably carried out under stirring; the rotation speed of stirring is preferably 500-1000 r/min; this step is carried out by hydrolysis to give a halohydrin solution, preferably a chlorohydrin solution.
Mixing the halohydrin solution with polyethylene polyamine, heating and reacting to obtain an intermediate product I; the mass ratio of polyethylene polyamine to halogenated epoxide is preferably (70-90): 38, a step of carrying out the process; in some embodiments provided herein, the mass ratio of polyethylene polyamine to halogenated epoxide is preferably 70:38, a step of carrying out the process; in some embodiments provided herein, the mass ratio of polyethylene polyamine to halogenated epoxide is preferably 80:38, a step of carrying out the process; in other embodiments provided by the present invention, the mass ratio of polyethylene polyamine to halogenated epoxide is preferably 90:38, a step of carrying out the process; the polyethylene polyamine is preferably one or more of diethylenetriamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine, more preferably tetraethylenepentamine; in this step the halohydrin is quaternized with polyethylene polyamine; the temperature of the heating reaction is preferably 60-90 ℃; the heating reaction time is preferably 1 to 2 hours; in the present invention, the reaction is preferably carried out under stirring; the stirring speed is preferably 500-1000 r/min.
Mixing the intermediate product I with dihaloethane, heating and reacting to obtain an intermediate product II; the dihaloethane is preferably dichloroethane; the mass ratio of the dihaloethane to the halogenated epoxide is preferably (40-60): 38, a step of carrying out the process; in some embodiments provided herein, the mass ratio of dihaloethane to halogenated epoxide is preferably 40:38, a step of carrying out the process; in some embodiments provided herein, the mass ratio of dihaloethane to halogenated epoxide is preferably 50:38, a step of carrying out the process; in some embodiments provided herein, the mass ratio of dihaloethane to halogenated epoxide is preferably 60:38, a step of carrying out the process; the temperature of the heating reaction is preferably 80-105 ℃; the heating reaction time is preferably 2-4 hours; in the present invention, the reaction is preferably carried out under stirring; the stirring speed is preferably 500-1000 r/min. By introducing dihaloethane, the C atom and N atom can be directly connected, the high temperature stability of the molecule is increased, and the temperature resistance of the polyamine is further improved.
Mixing the intermediate product II with polyethylene polyamine, heating and reacting to obtain an intermediate product III; the mass ratio of polyethylene polyamine to halogenated epoxide is preferably (140-200): 38, a step of carrying out the process; in some embodiments provided herein, the mass ratio of polyethylene polyamine to halogenated epoxide is preferably 140:38, a step of carrying out the process; in some embodiments provided herein, the mass ratio of polyethylene polyamine to halogenated epoxide is preferably 160:38, a step of carrying out the process; in some embodiments provided herein, the mass ratio of polyethylene polyamine to halogenated epoxide is preferably 180:38, a step of carrying out the process; in other embodiments provided by the present invention, the mass ratio of polyethylene polyamine to halogenated epoxide is preferably 200:38, a step of carrying out the process; the polyethylene polyamine is preferably one or more of diethylenetriamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine, more preferably tetraethylenepentamine; the temperature of the heating reaction is preferably 70-95 ℃; the heating reaction time is preferably 2-4 hours; in the present invention, the reaction is preferably carried out under stirring; the stirring speed is preferably 500-1000 r/min.
Adding acetic acid into the intermediate product III, and heating to perform a chain termination reaction to obtain polyamine with inhibition and solid phase cleaning functions; the mass ratio of the acetic acid to the halogenated epoxide is preferably (50-70): 38, a step of carrying out the process; in some embodiments provided herein, the mass ratio of acetic acid to halogenated epoxide is preferably 50:38, a step of carrying out the process; in some embodiments provided herein, the mass ratio of acetic acid to halogenated epoxide is preferably 60:38, a step of carrying out the process; in other embodiments provided herein, the mass ratio of acetic acid to halogenated epoxide is preferably 70:38, a step of carrying out the process; the temperature of the chain termination reaction is preferably 50-70 ℃; the heating reaction time is preferably 0.5 to 1 hour; in the present invention, the reaction is preferably carried out under stirring; the stirring speed is preferably 500-1000 r/min.
The preparation method provided by the invention has mild reaction conditions, takes water as a solvent, and has no waste water, waste gas and waste residue emission.
The invention also provides a drilling fluid which comprises the polyamine with the inhibition and solid phase cleaning functions.
In order to further illustrate the present invention, the following examples are provided to describe in detail a polyamine having both inhibition and solid phase cleaning, a process for its preparation and its use.
The reagents used in the examples below are all commercially available.
Example 1
Adding 38g of epichlorohydrin, 60g of water and 4g of concentrated sulfuric acid into a reaction kettle, controlling the stirring speed to be 500r/min, and reacting for 0.5h at the temperature of 85 ℃ to obtain a chlorohydrin solution; 70g of tetraethylenepentamine is added into the chlorohydrine solution to react for 1.0h at the temperature of 60 ℃ to obtain an intermediate product I; 40g of dichloroethane is added into the intermediate product I and reacts for 2.0h at the temperature of 80 ℃ to obtain an intermediate product II; 140g of tetraethylenepentamine is added into the intermediate product II to react for 2.0h at the temperature of 70 ℃ to obtain an intermediate product III; 50g of acetic acid is added into the intermediate product III, and the reaction is carried out for 0.5h at the temperature of 50 ℃ to generate chain termination reaction, thus obtaining reddish brown viscous transparent liquid, namely polyamine with the functions of inhibiting and cleaning solid phase. The product yield was 93.42%.
The polyamine with both inhibition and solid phase cleaning functions prepared in the embodiment 1 of the invention has a structure shown in a formula 1:
in the formula 1, m is 1-10, n is 3, R is CH 2 。
The polyamine having both inhibition and solid phase cleaning effects obtained in example 1 was analyzed by infrared spectroscopy, and the infrared spectrum thereof was shown in FIG. 1.
Example 2
Adding 38g of epoxy chlorobutane, 80g of water and 5g of concentrated hydrochloric acid into a reaction kettle, controlling the stirring speed to be 700r/min, and reacting for 1.0h at the temperature of 90 ℃ to obtain a chlorohydrin solution; 80g of tetraethylenepentamine is added into the chlorohydrine solution to react for 2.0h at the temperature of 70 ℃ to obtain an intermediate product I; 50g of dichloroethane is added into the intermediate product I and reacts for 3.0h at the temperature of 90 ℃ to obtain an intermediate product II; 160g of tetraethylenepentamine is added into the intermediate product II to react for 3.0h at the temperature of 80 ℃ to obtain an intermediate product III; 60g of acetic acid is added into the intermediate product III, and the reaction is carried out for 1.0h at the temperature of 60 ℃ to generate chain termination reaction, thus obtaining reddish brown viscous transparent liquid, namely polyamine with the functions of inhibiting and cleaning solid phase. The product yield was 92.87%.
The polyamine with both inhibition and solid phase cleaning functions prepared in the embodiment 2 of the invention has a structure shown in a formula 2:
in the formula 2, m is 1 to 10, n is 3, R is C 2 H 4 。
Example 3
Adding 38g of epichlorohydrin, 100g of water and 7g of p-toluenesulfonic acid into a reaction kettle, controlling the stirring speed to be 900r/min, and reacting for 1.0h at the temperature of 95 ℃ to obtain a chlorohydrin solution; 90g of tetraethylenepentamine is added into the chlorohydrine solution and reacts for 2.0h at the temperature of 80 ℃ to obtain an intermediate product I; 60g of dichloroethane is added into the intermediate product I and reacts for 4.0 hours at the temperature of 100 ℃ to obtain an intermediate product II; 180g of tetraethylenepentamine is added into the intermediate product II to react for 4.0h at the temperature of 90 ℃ to obtain an intermediate product III; 70g of acetic acid is added into the intermediate product III, and the mixture reacts for 1.0h at the temperature of 70 ℃ to generate chain termination reaction, thus obtaining reddish brown viscous transparent liquid, namely polyamine with the functions of inhibiting and cleaning solid phase. The product yield was 92.65%.
The polyamine with both inhibition and solid phase cleaning functions prepared in example 3 of the present invention has a structure shown in formula 3:
in the formula 3, m is 1-10, n is 3, R is CH 2 。
Example 4
Adding 38g of epichlorohydrin, 120g of water and 8g of dodecylbenzene sulfonic acid into a reaction kettle, controlling the stirring speed to be 1000r/min, and reacting for 1.0h at the temperature of 95 ℃ to obtain a chlorohydrin solution; 90g of tetraethylenepentamine is added into the chlorohydrine solution and reacts for 2.0h at the temperature of 90 ℃ to obtain an intermediate product I; 60g of dichloroethane is added into the intermediate product I and reacts for 4.0 hours at the temperature of 105 ℃ to obtain an intermediate product II; 200g of tetraethylenepentamine is added into the intermediate product II to react for 4.0h at the temperature of 95 ℃ to obtain an intermediate product III; 70g of acetic acid is added into the intermediate product III, and the mixture reacts for 1.0h at the temperature of 70 ℃ to generate chain termination reaction, thus obtaining reddish brown viscous transparent liquid, namely polyamine with the functions of inhibiting and cleaning solid phase. The product yield was 93.96%.
The polyamine with both inhibition and solid phase cleaning functions prepared in example 4 of the present invention has a structure shown in formula 4:
in the formula 4, m is 1-10, n is 3, R is CH 2 。
The polyamine with the effect of inhibiting and cleaning the solid phase, which is prepared in the embodiments 1 to 4 of the invention, is rolled for 16 hours at 200 ℃ in 4% of soil slurry (the mass of the polyamine with the effect of inhibiting and cleaning the solid phase is 1.0% of the mass of the soil slurry), and apparent viscosity AV and filtration loss FL are tested, and test results are shown in Table 1; the results of the rock debris recovery and relative inhibition rate test for the lime-soil slurry at 200 ℃ for 16 hours are shown in table 2, wherein the rock debris recovery rate of 1.0% of polyamine having both inhibition and solid phase cleaning effects (the polyamine having both inhibition and solid phase cleaning effects is 1% of distilled water mass) and the relative inhibition rate for the lime-soil slurry (the polyamine having both inhibition and solid phase cleaning effects is 1% of lime-soil slurry mass).
According to GB/T16783.1-2014 section 1, petroleum and Natural gas Industrial drilling fluid field test: the apparent viscosity and the fluid loss of the drilling fluid composition are tested according to the standard of water-based drilling fluid.
The recovery rate of the cuttings of the polyamine having both the inhibition and solid phase cleaning actions was evaluated as follows, and the primary recovery rate and the relative recovery rate of the cuttings were tested, specifically as follows:
pouring 350mL distilled water into an aging tank, adding polyamine with inhibiting and solid phase cleaning effects in an amount of 1% by mass of distilled water, drying 2.0-5.0 mm rock fragments at 103 ℃ for 4h, cooling to room temperature, and weighing G 0 Placing the G rock fragments into an aging tank, rolling for 16h at 200 ℃, cooling, taking out, recovering the rock fragments by using a sieve with the aperture of 0.42mm, drying for 4h at 103 ℃, cooling to room temperature, weighing and recovering the rock fragments, and recording the mass of the recovered rock fragments as G 1 The method comprises the steps of carrying out a first treatment on the surface of the Then putting the weighed recovered rock fragments into clear water, rolling for 2 hours at 200 ℃, cooling, taking out, recovering the rock fragments by using a sieve with the aperture of 0.42mm, drying for 4 hours at 103 ℃, cooling to room temperature, weighing and recovering the rock fragments, and recording the mass of the recovered rock fragments as G 2 The method comprises the steps of carrying out a first treatment on the surface of the Calculating the recovery rate R of the primary shale respectively 1 Recovery rate R of secondary shale 2 And relative shale recovery R:
R 1 =G 1 /G 0 ×100%;
R 2 =G 2 /G 0 ×100%;
R=R 2 /R 1 ×100%。
the relative inhibition rate of polyamine having both inhibition and solid phase cleaning effects on the lime soil slurry was evaluated according to the following method: taking 350mL of distilled water, adding 0.5% of sodium carbonate, dissolving, adding 10% of calcium bentonite, stirring at a high speed for 20min, rolling at 200 ℃ for 16h, cooling, taking out to obtain a calcium-earth base slurry, stirring at a high speed for 5min, and measuring the 100r/min reading of the calcium-earth base slurry as phi by using a six-speed rotational viscosimeter; taking 350mL of distilled water, adding 0.5% of sodium carbonate and 0.5% of polyamine sample with inhibiting and solid phase cleaning effects, fully dissolving, adding 10% of calcium bentonite, stirring at high speed for 20min, rolling at 200 ℃ for 16h, cooling, taking out, stirring at high speed for 5min, and measuring with a six-speed rotational viscosimeterA100 r/min reading for a lime-soil slurry of a polyamine having inhibition and solid phase cleaning effects is phi 1 The relative inhibition rate of the polyamine product with inhibition and solid phase cleaning functions to the lime soil is calculated according to the following formula:
wherein:
b-the relative inhibition rate of polyamine with inhibition and solid phase cleaning functions to the lime soil base slurry,%;
stabilizing reading when the rotating speed of the rotary viscometer of the phi-calcium soil-based slurry is 100 r/min;
Ф 1 the readings are stabilized at a rotational speed of 100r/min by adding a calcium earth-based slurry rotational viscometer which combines a polyamine inhibiting and solid phase cleaning action.
TABLE 1 rheological test results of polyamine samples with both inhibition and solid phase cleaning for 4% soil slurry
TABLE 2 polyamine sample rock debris recovery and relative inhibition test results with both inhibition and solid phase cleaning
As can be seen from the data in the table 1, after aging for 16 hours at 200 ℃,1.0% of polyamine with inhibition and solid phase cleaning functions has less influence on the apparent viscosity of the 4% soil slurry, and the change value of the apparent viscosity is less than or equal to 1.0 Pa.s;1.0% of polyamine sample with inhibiting and solid phase cleaning effects has small influence on the filtration loss of 4% of soil slurry, and the change value of the filtration loss is less than or equal to 0.6mL; the polyamine with the functions of inhibiting and cleaning the solid phase has better compatibility to soil slurry.
As can be seen from the data in Table 2, after aging at 200 ℃ for 16 hours, 1.0% of polyamine which has both inhibition and solid phase cleaning functions has a primary recovery rate of more than 97% and a relative recovery rate of more than 99%;1.0% of polyamine with the inhibiting and solid phase cleaning functions has a relative inhibiting rate of more than 97% on the calcareous soil base slurry, and shows that the polyamine with the inhibiting and solid phase cleaning functions has excellent strong inhibiting and collapse preventing capability on shale well walls and solid phase cleaning capability on drilling fluid.
Claims (9)
1. A polyamine having both inhibition and solid phase cleaning functions, characterized by having a structure represented by the formula (I):
wherein m is an integer of 1 to 10, n is an integer of 1 to 5, and R is a C1 to C5 alkylene group.
2. The polyamine of claim 1, wherein n is 3; the R is CH 2 Or C 2 H 4 。
3. A process for the preparation of a polyamine having both inhibition and solid phase cleaning properties according to claim 1 comprising:
s1) mixing halogenated epoxide, water and an acid catalyst, heating and reacting to obtain halogenated alcohol solution;
s2) mixing the halohydrin solution with polyethylene polyamine, heating and reacting to obtain an intermediate product I;
s3) mixing the intermediate product I with dihaloethane, heating and reacting to obtain an intermediate product II;
s4) mixing the intermediate product II with polyethylene polyamine, heating and reacting to obtain an intermediate product III;
s5) adding acetic acid into the intermediate product III, and heating to generate a chain termination reaction to obtain the polyamine with the functions of inhibiting and cleaning a solid phase.
4. A process according to claim 3, wherein the halogenated epoxide is selected from C3 to C7 chloroepoxides; the acid catalyst is selected from one or more of concentrated sulfuric acid, concentrated hydrochloric acid, p-toluenesulfonic acid and dodecylbenzenesulfonic acid; the polyethylene polyamine is selected from one or more of diethylenetriamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine; the dihaloethane is selected from dichloroethane.
5. A process according to claim 3, wherein the halogenated epoxide is selected from epichlorohydrin and/or epichlorohydrin; the polyethylene polyamine is selected from tetraethylenepentamine.
6. A process according to claim 3, wherein the mass ratio of halogenated epoxide, water to acid catalyst is 38: (60-120): (4-8); the mass ratio of the polyethylene polyamine to the halogenated epoxide in the step S2) is (70-90): 38, a step of carrying out the process; the mass ratio of the dihaloethane to the halogenated epoxide is (40-60): 38, a step of carrying out the process; the mass ratio of polyethylene polyamine to halogenated epoxide in the step S4) is (140-200): 38, a step of carrying out the process; the mass ratio of the acetic acid to the halogenated epoxide is (50-70): 38.
7. the method according to claim 3, wherein the heating reaction in the step S1) is carried out at a temperature of 85 to 95 ℃; the heating reaction time is 0.5-1 h;
the temperature of the heating reaction in the step S2) is 60-90 ℃; the heating reaction time is 1-2 h;
the temperature of the heating reaction in the step S3) is 80-105 ℃; the heating reaction time is 2-4 h;
the temperature of the heating reaction in the step S4) is 70-95 ℃; the heating reaction time is 2-4 h;
the temperature of the chain termination reaction in the step S5) is 50-70 ℃; the heating reaction time is 0.5-1 h.
8. The process according to claim 3, wherein the reactions in steps S1) to S5) are carried out with stirring; the stirring speed is 500-1000 r/min.
9. A drilling fluid comprising the polyamine having both inhibition and solid phase cleaning effects according to any one of claims 1 to 2 or the polyamine having both inhibition and solid phase cleaning effects prepared by the method of any one of claims 3 to 8.
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