CN111188606B - Low-temperature expandable graphite for steam injection channeling sealing of heavy oil reservoir and preparation method and application thereof - Google Patents
Low-temperature expandable graphite for steam injection channeling sealing of heavy oil reservoir and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 137
- 239000010439 graphite Substances 0.000 title claims abstract description 136
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 136
- 230000005465 channeling Effects 0.000 title claims abstract description 32
- 238000007789 sealing Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000295 fuel oil Substances 0.000 title claims abstract description 14
- 238000010793 Steam injection (oil industry) Methods 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 65
- 238000000034 method Methods 0.000 claims abstract description 52
- 239000002253 acid Substances 0.000 claims abstract description 25
- 239000007800 oxidant agent Substances 0.000 claims abstract description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 20
- -1 alkali metal salt Chemical class 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 44
- 238000010008 shearing Methods 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 19
- 239000012286 potassium permanganate Substances 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 11
- 239000003125 aqueous solvent Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 238000011084 recovery Methods 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 229910001963 alkali metal nitrate Inorganic materials 0.000 claims description 4
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 229910021645 metal ion Chemical group 0.000 claims description 3
- 229910001508 alkali metal halide Inorganic materials 0.000 claims description 2
- 150000008045 alkali metal halides Chemical class 0.000 claims description 2
- 229910000318 alkali metal phosphate Inorganic materials 0.000 claims description 2
- 229910052936 alkali metal sulfate Inorganic materials 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 238000011282 treatment Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 8
- 239000010779 crude oil Substances 0.000 abstract description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 230000008569 process Effects 0.000 description 15
- 238000009830 intercalation Methods 0.000 description 12
- 230000002687 intercalation Effects 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- 239000004317 sodium nitrate Substances 0.000 description 10
- 235000010344 sodium nitrate Nutrition 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 238000000967 suction filtration Methods 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 7
- 239000006260 foam Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000000084 colloidal system Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 235000015110 jellies Nutrition 0.000 description 4
- 239000008274 jelly Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000010795 Steam Flooding Methods 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- OBESRABRARNZJB-UHFFFAOYSA-N aminomethanesulfonic acid Chemical compound NCS(O)(=O)=O OBESRABRARNZJB-UHFFFAOYSA-N 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000000638 stimulation Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000012224 working solution Substances 0.000 description 1
Images
Classifications
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
- E21B43/24—Enhanced recovery methods for obtaining hydrocarbons using heat, e.g. steam injection
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/21—After-treatment
- C01B32/22—Intercalation
- C01B32/225—Expansion; Exfoliation
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B33/00—Sealing or packing boreholes or wells
- E21B33/10—Sealing or packing boreholes or wells in the borehole
- E21B33/12—Packers; Plugs
Landscapes
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mining & Mineral Resources (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Fluid Mechanics (AREA)
- Physics & Mathematics (AREA)
- Geochemistry & Mineralogy (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to the field of oilfield chemistry, in particular to low-temperature expandable graphite suitable for steam injection channeling sealing of a heavy oil reservoir and a preparation method and application thereof. A method for preparing low-temperature expandable graphite, which is characterized by comprising the following steps: a compound represented by the formula (1), an oxidizing agent, an acid, an alkali metal salt and graphite are subjected to a contact reaction. The low-temperature expandable graphite system has the characteristics of high expansion rate, good thermal stability, portability, stratum entering and flexibility of graphite, can improve the steam channeling sealing effect and prolong the effective service life of a channeling sealing agent, reduces the treatment cost and realizes the high-efficiency output of crude oil.
Description
Technical Field
The invention relates to the field of oilfield chemistry, in particular to low-temperature expandable graphite for steam injection and channeling sealing of a heavy oil reservoir and a preparation method and application thereof.
Background
Thermal oil recovery is a method mainly adopted in the process of thick oil recovery, and steam flooding and steam stimulation are two common thermal recovery modes. After the stratum is subjected to long-term steam treatment, a steam dominant seepage channel is easily formed, so that injected steam flows along the channel, residual oil cannot be effectively swept, and energy waste is caused. Therefore, steam lock-out is a problem that must be addressed during steam flooding/steam stimulation.
The channeling sealing agent for steam channeling sealing at present mainly comprises high-temperature jelly, high-temperature foam and inorganic rigid particles. The jelly glue channeling sealing agent plays a role in injecting mixed gel forming liquid (mixed solution of polymer and cross-linking agent) into a stratum to form solid or semi-solid jelly under the stratum condition. The gel liquid preferentially enters the high permeable layer, so that the steam channeling channel is blocked. The foam channeling sealing agent mainly utilizes the Jamin effect of foam in pores of a stratum, the foam injected into the stratum enters a steam channeling channel with higher permeability preferentially for sealing, and the foam is unstable when meeting oil and is easy to defoam, so that an oil layer cannot be sealed. The inorganic rigid particles are injected into the stratum along with the carrier fluid, and are accumulated in pores to bridge at the throat to realize the blocking of a steam channeling channel.
Although the channeling sealing agent is applied in the steam channeling sealing process and achieves certain field effect, the defects are also exposed. The requirements of the jelly and the foam channeling sealing agent on the temperature of the oil reservoir are high. The gel is quick in gelling under high temperature, easy to age and dehydrate, low in plugging strength and difficult to realize deep regulation of stratum. And the gelling liquid is sheared by the sieve tube, the perforation holes and the formation pores in the injection process, and the gelling performance is reduced. The foam is unstable at high temperature, and is easy to defoam, and the channeling sealing effect is influenced. The formation temperature is high (150-. The inorganic rigid particles (such as superfine cement, clay and the like) have poor injectivity and migration performance in the stratum, are easy to deposit on a well wall or a near-well zone in the injection process, are sensitive to temperature, and have short curing time at high temperature, so certain engineering risk is caused to construction, and the channeling sealing effect is poor.
At present, the conditions of heavy oil reservoirs are different, which not only shows different conditions of reservoirs (different permeability ranges and different heterogeneity), but also shows different well conditions (open hole, perforation and sand control screen pipe).
Disclosure of Invention
Aiming at the defects of the existing steam flooding/steam stimulation channeling sealing agent, the invention aims to provide low-temperature expandable graphite suitable for steam injection channeling sealing of a heavy oil reservoir and a preparation method and application thereof. By means of the characteristics of high expansion rate, good thermal stability, portability, stratum entering and flexibility of graphite, the low-temperature expandable graphite system can improve the steam channeling sealing effect, prolong the effective service life of the channeling sealing agent, reduce the treatment cost and realize the high-efficiency production of crude oil.
In order to achieve the above object, the present invention provides a method for preparing low temperature expandable graphite suitable for steam injection channeling sealing of heavy oil reservoirs, which comprises: in an aqueous solvent, carrying out contact reaction on a compound shown as a formula (1), an oxidant, an acid, an alkali metal salt and graphite;
formula (1)
L is a connecting bond or alkylene of C1-C4; m is hydrogen or a metal ion.
In a second aspect, the present invention provides a low temperature expandable graphite prepared by the above method.
The third aspect of the invention provides the application of the low-temperature expandable graphite as a steam channeling sealing agent in oil reservoir exploitation.
The fourth aspect of the invention provides a heavy oil thermal recovery method, which comprises the step of adopting the low-temperature expandable graphite as a steam channeling sealing agent.
Compared with the prior art, the invention has the following advantages:
(1) the low-temperature expandable graphite has low-temperature expansibility, namely can be expanded at the low temperature of 150 ℃ and 300 ℃ compared with the traditional expandable graphite (the initial expansion temperature is higher than 300 ℃).
(2) The low-temperature expandable graphite has wide application range, and can be used in the steam channeling sealing process of various heterogeneous heavy oil reservoirs (different permeability ranges, different heterogeneity, open hole wells, screen wells and the like).
(3) The low-temperature expandable graphite has the advantages of high expansion rate, good thermal stability, good chemical stability, portability, stratum entering and flexibility.
(4) The preparation method and the using process of the low-temperature expandable graphite are simple, the working solution is convenient to prepare on site, and the raw materials and the construction cost are low.
(5) The low-temperature expandable graphite has flexibility and self-lubricating property, so that the colloid mill is protected in a physical shearing stage, a pipe body and an eyelet cannot be abraded in the using process, the low-temperature expandable graphite is not easy to be retained and deposited in the eyelet or a near-wellbore area, and the construction risk is low.
Drawings
FIG. 1 is a graph showing the macroscopic expansion effect of the expandable graphite at 150 ℃ obtained in the chemical reaction stage of example 2;
FIG. 2 is a graph showing the macroscopic expansion effect of the expandable graphite at 300 ℃ obtained in the chemical reaction stage of example 2;
FIG. 3 is a comparison of the morphology of the expandable graphite obtained during the chemical reaction stage of example 2 before and after expansion at 300 ℃;
FIG. 4 is the particle size of the expandable graphite as a function of shear time under 20Hz colloid mill shear conditions of example 2;
FIG. 5 is an IR spectrum of crystalline flake graphite, expandable graphite obtained in the chemical reaction stage and expanded graphite obtained after the expansion in example 2.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a preparation method of low-temperature expandable graphite suitable for steam injection channeling sealing of a heavy oil reservoir, which comprises the following steps: in an aqueous solvent, carrying out contact reaction on a compound shown as a formula (1), an oxidant, an acid, an alkali metal salt and graphite;
formula (1)
L is a connecting bond or alkylene of C1-C4; m is hydrogen or a metal ion.
According to the present invention, by treating graphite with the compound represented by formula (1) of the present invention, an oxidizing agent, an acid and an alkali metal salt, it is possible to sufficiently intercalate graphite to obtain a graphite system that can be highly expanded at a lower temperature, and it is understood that the compound represented by formula (1), the oxidizing agent, the acid and the alkali metal salt are intercalation agents for graphite in the present invention.
According to the present invention, in order to obtain a better complexing effect between the intercalants and to obtain a better performance of the low temperature expandable graphite system, it is preferable that the compound represented by the formula (1) is used in an amount of 20 to 150 parts by weight, the oxidizing agent is used in an amount of 1 to 50 parts by weight, the acid is used in an amount of 100 parts by weight, and the alkali metal salt is used in an amount of 10 to 80 parts by weight, relative to 100 parts by weight of graphite. More preferably, the compound represented by the formula (1) is used in an amount of 30 to 100 parts by weight, the oxidizing agent is used in an amount of 5 to 40 parts by weight, the acid is used in an amount of 150 to 400 parts by weight, and the alkali metal salt is used in an amount of 20 to 50 parts by weight, relative to 100 parts by weight of graphite. Still more preferably, the compound represented by the formula (1) is used in an amount of 40 to 80 parts by weight, the oxidizing agent is used in an amount of 10 to 25 parts by weight, the acid is used in an amount of 200 to 300 parts by weight, and the alkali metal salt is used in an amount of 25 to 40 parts by weight, relative to 100 parts by weight of graphite. Particularly preferably, the compound represented by the formula (1) is used in an amount of 50 to 80 parts by weight, the oxidizing agent is used in an amount of 10 to 20 parts by weight, the acid is used in an amount of 250 to 300 parts by weight, and the alkali metal salt is used in an amount of 30 to 40 parts by weight, relative to 100 parts by weight of graphite. Wherein the amount of acid is based on the acid molecule, and the water content is removed.
According to the present invention, although the intercalation of graphite with other agents can be carried out using the compound represented by formula (1) to obtain usable low-temperature expandable graphite, it is preferable that in formula (1), L is a bond, -CH2-、-CH2CH2-、-CH2CH2CH2-、-CH(CH3)CH2-、-CH2CH(CH3)-、-C(CH3)2-or-CH2CH2CH2CH2-; m isHydrogen, Li, Na or K.
Among them, specific examples of the compound represented by the formula (1) may be selected from compounds represented by the following formulae:
formula (1-1): in the formula (1), L is a connecting bond, and M is hydrogen (namely sulfamic acid);
formula (1-2): in the formula (1), L is a connecting bond, and M is Na;
formula (1-3): in the formula (1), L is a connecting bond, and M is K;
formula (1-4): in the formula (1), L is-CH2-, M is hydrogen (i.e. aminomethane sulfonic acid);
formula (1-5): in the formula (1), L is-CH2-, M is Na;
formula (1-6): in the formula (1), L is-CH2-, M is K;
formula (1-7): in the formula (1), L is-CH2CH2-, M is hydrogen;
formula (1-8): in the formula (1), L is-CH2CH2-, M is Na;
formula (1-9): in the formula (1), L is-CH2CH2-, M is K.
According to the present invention, the oxidant can be selected from a variety of oxidants, but in order to better match the graphite intercalation process, preferably the oxidant is one or more of potassium permanganate, potassium dichromate, hydrogen peroxide, sulfuric acid, and perchloric acid, more preferably potassium permanganate.
According to the invention, the acid is preferably a strong acid to better match other reagents for the intercalation process of graphite, preferably the acid is one or more of perchloric acid, sulfuric acid, nitric acid, hydrochloric acid and acetic acid, more preferably perchloric acid. Wherein the acid is preferably provided in the form of a concentrated acid, for example perchloric acid is provided as concentrated perchloric acid having a concentration of 70-73% by weight, typically 72% by weight; the sulfuric acid is provided as 97-99% concentrated sulfuric acid, typically 98% by weight; the nitric acid is provided as concentrated nitric acid at 65-68 wt%, typically 67 wt%; hydrochloric acid is provided as concentrated hydrochloric acid in the range 34-37% by weight, typically 36% by weight; acetic acid is provided as glacial acetic acid in an amount greater than 99.7% by weight, typically 99.8% by weight.
According to the present invention, the alkali metal salt may be one or more of an alkali metal nitrate, an alkali metal halide, an alkali metal sulfate, and an alkali metal phosphate. In order to obtain a better complexing effect with other agents, the alkali metal salt is preferably an alkali metal nitrate, such as one or more of sodium nitrate, potassium nitrate, and the like.
According to the present invention, preferably, the conditions of the contact reaction include: the temperature is 30-60 deg.C, and the time is 30-120 min. More preferably, the conditions of the contact reaction include: the temperature is 30-50 deg.C, and the time is 60-100 min. The contact reaction is preferably carried out under ultrasonic conditions, which is favorable for full contact between reactants and the intercalation agent to enter the graphite carbon layer, so that the oxidation intercalation reaction is more full.
In a preferred embodiment of the present invention, the contact reaction comprises a first contact reaction and a second contact reaction; the first contact reaction comprises: subjecting a compound represented by formula (1), the oxidizing agent, and the graphite to a first contact reaction in an aqueous solvent; the second contact reaction comprises: subjecting the product of said first contact reaction to a second contact reaction with said acid and said alkali metal salt in an aqueous solvent.
In this preferable case, the compound represented by formula (1) and the oxidant may be combined to form a first oxidation intercalant, and the first oxidation intercalant and graphite are subjected to a first contact reaction, so as to obtain a graphite system after the first oxidation intercalant; then combining the acid and the alkali metal salt to form a second oxidation intercalation agent, and carrying out a second contact reaction on the second oxidation intercalation agent and the graphite system subjected to the first oxidation intercalation to ensure that the graphite system is subjected to a second oxidation intercalation; after two-step contact reaction, a graphite system of secondary oxidation intercalation is obtained, and the graphite system has better low-temperature expansibility.
According to this preferred aspect, preferably, the conditions of the first contact reaction include: the temperature is 30-60 deg.C, and the time is 20-60 min; the conditions of the second contact reaction include: the temperature is 30-60 deg.C, and the time is 30-120 min. More preferably, the conditions of the first contact reaction include: the temperature is 35-50 deg.C, and the time is 25-45 min; the conditions of the second contact reaction include: the temperature is 35-50 deg.C, and the time is 50-80 min.
Wherein the first contact reaction and the second contact reaction are preferably carried out under the action of ultrasound so as to make the intercalation treatment more sufficient.
The contact reaction of the present invention is carried out in an aqueous solvent, which may be water or an aqueous solution containing a solvent that does not affect the contact reaction of the present invention. Wherein the aqueous solvent may be provided by an aqueous solution of another substance.
Wherein the compound represented by the formula (1) and the oxidizing agent are provided in the form of an aqueous solution, preferably, the amount of water is 200-500 parts by weight, preferably 250-350 parts by weight, relative to 100 parts by weight of the compound represented by the formula (1) and the oxidizing agent.
In order to make the second contact reaction more smoothly, the product after the first contact reaction can be subjected to solvent removal treatment after the first contact reaction; in addition, the product is dehydrated (for example, by suction filtration), washed with water and dried after the second contact reaction.
According to the present invention, in order to obtain low temperature expandable graphite with more suitable particle size, preferably, the method comprises: and shearing the product after the contact reaction to ensure that the particle size of the graphite is 30-150 mu m. Wherein the shearing treatment can be carried out in a colloid mill, and the shearing conditions comprise: the power is 10-50Hz (preferably 20-45Hz), and the time is 1-30min (preferably 5-20 min). Before shearing, the product after contact reaction and water are required to form graphite dispersion liquid, and the weight ratio of the water to the product after contact reaction can be 20-80: 1, preferably 40 to 60: 1.
according to the present invention, in order to obtain a more pure low temperature expandable graphite of the present invention, after the shearing treatment, the resultant product is dehydrated (e.g., suction filtration), dried to obtain the low temperature expandable graphite of the present invention.
In a second aspect, the present invention provides a low temperature expandable graphite prepared by the above method.
The third aspect of the invention provides the application of the low-temperature expandable graphite as a steam channeling sealing agent in oil reservoir exploitation.
The fourth aspect of the invention provides a heavy oil thermal recovery method, which comprises the step of adopting the low-temperature expandable graphite as a steam channeling sealing agent.
The low-temperature expandable graphite has excellent expansibility at a lower temperature, for example, the expansion can be carried out between 150 ℃ and 300 ℃, and the expansion multiple is higher.
The present invention will be described in detail below by way of examples.
Example 1
This example illustrates the low temperature expandable graphite of the present invention and its method of preparation.
(1) Stirring and mixing an aqueous solution containing sulfamic acid and potassium permanganate (the content of sulfamic acid is 5g, the content of potassium permanganate is 1g and the dosage of water is 30g) with 10g of crystalline flake graphite (60-mesh crystalline flake graphite purchased from Qingdao Henhuda graphite products Co., Ltd.) for 5min, then placing the mixture at 40 ℃ for ultrasonic reaction for 30min, taking out the mixture, separating out reaction waste liquid through suction filtration, and taking the remainder as graphite after the first contact reaction;
(2) stirring and mixing perchloric acid dispersion liquid containing sodium nitrate (the content of the sodium nitrate is 4g, the perchloric acid is concentrated perchloric acid with the concentration of 72 weight percent, and the dosage of the perchloric acid is 30g) with the graphite after the first contact reaction for 5min, then carrying out ultrasonic reaction at 40 ℃ for 1h, and taking out; carrying out suction filtration on the system, washing the remainder with water until the pH value of the filtrate is 5-7, and then drying at 60 ℃ to obtain graphite after the second contact reaction;
(3) adding 10g of the product obtained in the step (2) into 500g of water at room temperature (about 25 ℃), and stirring for 2min to disperse the graphite after the second contact reaction; pouring the obtained dispersion liquid into a colloid mill, and circularly shearing for 20min under the shearing condition of 20 Hz; the water removed by suction filtration after shearing was removed, and the residue was dried at 60 ℃ to obtain expandable graphite G1 having a particle size of 61.3 μm.
Example 2
This example illustrates the low temperature expandable graphite of the present invention and its method of preparation.
The process of example 1 was followed except that in step (1), the aqueous solution containing sulfamic acid and potassium permanganate had an sulfamic acid content of 8g, a potassium permanganate content of 2g, and 25g of water; finally obtaining expandable graphite G2 with the grain diameter of 60.1 mu m; wherein, the change curve of the particle size of the graphite along with the shearing time under the shearing condition of the 20Hz colloid mill is also measured in the process of the step (3), as shown in figure 4.
Example 3
This example illustrates the low temperature expandable graphite of the present invention and its method of preparation.
(1) Stirring and mixing an aqueous solution containing aminomethane sulfonic acid and potassium permanganate (the content of the aminomethane sulfonic acid is 5g, the content of the potassium permanganate is 1g, and the using amount of water is 25g) and 10g of crystalline flake graphite (60-mesh crystalline flake graphite purchased from Qingdao Henhun Daoka graphite products Co., Ltd.) for 5min, then placing the mixture at 45 ℃ for ultrasonic reaction for 40min, taking out the mixture, separating out reaction waste liquid through suction filtration, and taking the remainder as graphite after the first contact reaction;
(2) stirring and mixing perchloric acid dispersion liquid containing sodium nitrate (the content of the sodium nitrate is 3g, the perchloric acid is concentrated perchloric acid with the concentration of 72 weight percent, and the dosage of the perchloric acid is 30g) with the graphite after the first contact reaction for 5min, then carrying out ultrasonic reaction at 45 ℃ for 80min, and taking out; carrying out suction filtration on the system, washing the remainder with water until the pH value of the filtrate is 5-7, and then drying at 60 ℃ to obtain graphite after the second contact reaction;
(3) adding 10g of the product obtained in the step (2) into 500g of water at room temperature (about 25 ℃), and stirring for 2min to disperse the graphite after the second contact reaction; pouring the obtained dispersion liquid into a colloid mill, and circularly shearing for 15min under the shearing condition of 40 Hz; the water after shearing was removed by suction filtration, and the residue was dried at 60 ℃ to obtain expandable graphite G3 having a particle size of 35.3 μm.
Example 4
This example illustrates the low temperature expandable graphite of the present invention and its method of preparation.
The method of embodiment 2, except that in step (3), the shearing conditions comprise: circularly shearing for 1min under the shearing condition of 20 Hz; the expandable graphite G4 with a particle size of 141.5 μm was finally obtained.
Example 5
This example illustrates the low temperature expandable graphite of the present invention and its method of preparation.
The process of example 2 was followed except that 40g of concentrated nitric acid having a concentration of 67% by weight was used in step (2) in place of the concentrated perchloric acid; finally, expandable graphite G5 with the particle size of 62.5 μm was obtained.
Example 6
This example illustrates the low temperature expandable graphite of the present invention and its method of preparation.
The process of example 2 was followed except that in step (2), concentrated perchloric acid was replaced with 30g of concentrated sulfuric acid having a concentration of 98% by weight; finally, expandable graphite G6 with a particle size of 59.3 μm was obtained.
Example 7
This example illustrates the low temperature expandable graphite of the present invention and its method of preparation.
The process of example 2 was followed except that in step (2) an equal part by weight of potassium chloride was used in place of sodium nitrate; finally, expandable graphite G7 having a particle size of 63.7 μm was obtained.
Example 8
This example illustrates the low temperature expandable graphite of the present invention and its method of preparation.
The process of example 2 was followed except that in step (2) an equal part by weight of sodium sulfate was used in place of sodium nitrate; finally, expandable graphite G8 with the particle size of 62.4 μm was obtained.
Example 9
This example illustrates the low temperature expandable graphite of the present invention and its method of preparation.
According to the method described in example 2, except that the graphite is subjected to a primary contact reaction with an aqueous solution containing sulfamic acid and potassium permanganate and a dispersion of perchloric acid containing sodium nitrate, the graphite is treated as follows:
stirring and mixing an aqueous solution containing sulfamic acid and potassium permanganate (the content of sulfamic acid is 8g, the content of potassium permanganate is 2g and the amount of water is 25g) and a perchloric acid dispersion liquid containing sodium nitrate (the content of sodium nitrate is 4 g; perchloric acid is concentrated perchloric acid with the concentration of 72 weight percent and the amount of 30g) with 10g of crystalline flake graphite (the crystalline flake graphite which is purchased from Qingdao Henhun Daoka graphite product Co., Ltd. and has the particle size of 60 meshes) for 5min, placing the mixture at 40 ℃ for ultrasonic reaction for 1.5h, taking the mixture out, removing water by suction filtration, washing the remainder until the pH of the filtrate is 5-7, and drying the residue at 60 ℃ to obtain graphite; then, shearing the graphite according to the step (3) of the embodiment 2; finally, expandable graphite G9 having a particle size of 61.9 μm was obtained.
Comparative example 1
According to the method described in example 2, except that, instead of the step (2), the product of the step (1) is directly filtered by mechanical energy, the residue is washed with water to a filtrate pH of 5 to 7, and then dried at 60 ℃ to obtain graphite, and then subjected to a shearing treatment according to the step (3) of example 2; the expandable graphite DG1 having a particle size of 58.6 μm was obtained.
Comparative example 2
According to the method of example 2, except that, instead of step (1), the commercially available flake graphite was directly subjected to the treatments of steps (2) and (3) in this order; the expandable graphite DG2 having a particle size of 57.8 μm was obtained.
Test example 1
Initial expansion temperature measurement: placing expandable graphite with the apparent volume of 2mL in a quartz glass tube, then placing the quartz glass tube in a high-temperature kettle, gradually increasing the setting temperature (100 + 350 ℃) of the high-temperature kettle until the volume of the expandable graphite is increased by more than 1.2 times after the expandable graphite is aged for 24 hours at a certain temperature, wherein the temperature is the initial expansion temperature of the expandable graphite; the results are shown in table 1 below.
TABLE 1
| Graphite | Initial expansion temperature (. degree. C.) |
| G1 | 180 |
| |
150 |
| G3 | 160 |
| |
150 |
| |
200 |
| |
250 |
| |
200 |
| G8 | 190 |
| G9 | 180 |
| DG1 | Does not expand |
| DG2 | 280 |
As can be seen from Table 1, the expandable graphite of the present invention can be expanded at lower temperatures, particularly in the temperature range of 150 ℃ to 300 ℃.
Test example 2
And (3) measurement of swelling degree: taking expandable graphite with the apparent volume of 2mL, placing the expandable graphite in a quartz glass tube, then placing the tube in a high-temperature kettle at 300 ℃, taking out the volume after 24h, and measuring the expansion degree at 300 ℃, wherein the results are shown in Table 2, the volume of the graphite product G2 obtained in example 2 before and after expansion at 150 ℃ is shown in figure 1, and the comparison graphs of the volume of the graphite before and after expansion at 300 ℃ and the morphology of the graphite are shown in figures 2 and 3 respectively; additionally, the Fourier infrared plots of the commercially available flake graphite before expansion, the graphite product G2 obtained in example 2 before expansion and after expansion are shown in FIG. 5.
The degree of expansion is the volume of graphite after expansion/the volume of graphite before expansion.
TABLE 2
| Graphite | Degree of expansion (300 ℃ C.) |
| Commercially |
1 |
| G1 | 19 |
| G2 | 22 |
| G3 | 16 |
| G4 | 24 |
| G5 | 15 |
| G6 | 7 |
| G7 | 13 |
| G8 | 14 |
| G9 | 15 |
| |
1 |
| |
2 |
It can be seen from table 2 that the expandable graphite of the present invention can achieve a better expansion effect at a lower temperature.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (17)
1. A preparation method of low-temperature expandable graphite suitable for steam injection channeling sealing of heavy oil reservoirs is characterized by comprising the following steps: in an aqueous solvent, carrying out contact reaction on a compound shown as a formula (1), an oxidant, an acid, an alkali metal salt and graphite; the contact reaction comprises a first contact reaction and a second contact reaction; the first contact reaction comprises: subjecting a compound represented by formula (1), the oxidizing agent, and the graphite to a first contact reaction in an aqueous solvent; the second contact reaction comprises: subjecting the product of said first contact reaction to a second contact reaction with said acid and said alkali metal salt in an aqueous solvent;
formula (1)
L is a connecting bond or alkylene of C1-C4; m is hydrogen or a metal ion.
2. The method as claimed in claim 1, wherein the compound represented by the formula (1) is used in an amount of 20 to 150 parts by weight, the oxidizing agent is used in an amount of 1 to 50 parts by weight, the acid is used in an amount of 100 parts by weight, and the alkali metal salt is used in an amount of 10 to 80 parts by weight, relative to 100 parts by weight of graphite.
3. The method as claimed in claim 2, wherein the compound represented by the formula (1) is used in an amount of 30 to 100 parts by weight, the oxidizing agent is used in an amount of 5 to 40 parts by weight, the acid is used in an amount of 150 to 400 parts by weight, and the alkali metal salt is used in an amount of 20 to 50 parts by weight, relative to 100 parts by weight of graphite.
4. The method as claimed in claim 3, wherein the compound represented by the formula (1) is used in an amount of 40 to 80 parts by weight, the oxidizing agent is used in an amount of 10 to 25 parts by weight, the acid is used in an amount of 200 to 300 parts by weight, and the alkali metal salt is used in an amount of 25 to 40 parts by weight, relative to 100 parts by weight of graphite.
5. The method according to any one of claims 1 to 4, wherein, in the formula (1), L is a bond, -CH2-、-CH2CH2-、-CH2CH2CH2-、-CH(CH3)CH2-、-CH2CH(CH3)-、-C(CH3)2-or-CH2CH2CH2CH2-; m is hydrogen, Li, Na or K.
6. The method of claim 5, wherein the oxidizing agent is one or more of potassium permanganate, potassium dichromate, hydrogen peroxide, sulfuric acid, and perchloric acid.
7. The method of claim 6, wherein the oxidizing agent is potassium permanganate.
8. The method of claim 5, wherein the acid is one or more of perchloric acid, sulfuric acid, nitric acid, hydrochloric acid, and acetic acid.
9. The method of claim 8, wherein the acid is perchloric acid.
10. The method of claim 5, wherein the alkali metal salt is one or more of an alkali metal nitrate, an alkali metal halide, an alkali metal sulfate, and an alkali metal phosphate.
11. The method of claim 10, wherein the alkali metal salt is an alkali metal nitrate.
12. The method of any one of claims 1-4 and 6-11, wherein the conditions of the first contact reaction comprise: the temperature is 30-60 deg.C, and the time is 20-60 min; the conditions of the second contact reaction include: the temperature is 30-60 deg.C, and the time is 30-120 min.
13. The method of any of claims 1-4 and 6-11, wherein the method comprises: and shearing the product after the contact reaction to ensure that the particle size of the graphite is 30-150 mu m.
14. The method of any of claims 1-4 and 6-11, wherein the graphite is flake graphite.
15. A low temperature expandable graphite made by the method of any one of claims 1-14.
16. Use of the low temperature expandable graphite of claim 15 as a steam channeling agent in reservoir recovery.
17. A heavy oil thermal recovery method comprising using the low temperature expandable graphite of claim 15 as a steam channeling agent for heavy oil reservoirs.
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