CN110791268A - Delayed crosslinking gel with interpenetrating network structure and preparation method thereof - Google Patents
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Abstract
A delayed crosslinking gel with interpenetrating network structure and its preparation method, it is by the weight percent first thickener 0.1 to 10%, the second thickener 0.1 to 20%, cross-linking agent 0.1 to 1%, PH regulator 0.05 to 1%, bactericide 0.01 to 1%, charge control agent 0.1 to 1%, ethanediol 10 to 40%, the others are water to formulate into; preparation: dissolving a first thickening agent in water, mixing, adding a pH regulator and a bactericide, and uniformly mixing; adding ethylene glycol, a charge regulator and a cross-linking agent into the mixed solution in the first step, and uniformly mixing; after the viscosity of the mixed solution reaches a fixed value, injecting the mixed solution into a petroleum pipeline to be poured to form a three-dimensional cross-linked network; thirdly, pouring a mixture of a second thickening agent, a cross-linking agent and water into two ends of the petroleum pipeline, so that the gel formed by the second thickening agent permeates into a gel system of the first thickening agent poured into the petroleum pipeline to form the delayed cross-linked gel with an interpenetrating network structure; the gel has good temperature resistance, and realizes effective plugging of the jumper pipe of the underwater oil-gas pipeline.
Description
Technical Field
The invention relates to a delayed crosslinking gel with an interpenetrating network structure and a preparation method thereof.
Background
With the increasing depletion of global land oil resources, people are beginning to turn their eyes to the ocean. It is estimated that the world reserves of oil and gas resources are likely 1/3 in continental racks, 1/3 in deep sea. Therefore, the marine oil will gradually replace the land oil to become the main source of future human oil and gas resources. During the development of a marine oil and gas field, wet natural gas forms Natural Gas Hydrates (NGH) in the gas collection pipeline under certain temperature and pressure conditions. Natural Gas Hydrate (NGH) is an ice-like cage crystal of hydrocarbon gas molecules formed by hydrogen bonding of water molecules, also known as combustible ice.
Hydrate problems are particularly acute for offshore field development and deep sea transport of oil and gas. The main reason is that both the water temperature and pressure conditions at the seabed are well suited for hydrate formation. With the increase of water depth, the hydrate forming condition is easily met under the condition of high pressure. Once the hydrate blocks equipment such as pipeline valves, the normal operation of production can be seriously influenced, and huge economic loss is caused. Therefore, how to prevent the generation of hydrate and solve the problem of hydrate blockage of underwater equipment are always concerned by the marine oil and gas industry and are also the problems which need to be broken through urgently in the industry.
The NGH inhibition methods mainly include two inhibition methods, thermodynamic and kinetic. The thermodynamic method is characterized in that the system does not have the thermodynamic condition for generating hydrate by dehydration, heating, pressure reduction and addition of a thermodynamic inhibitor. The kinetic inhibition principle is that the hydrate is controlled by adding a low-dose hydrate inhibitor and changing the kinetic conditions of hydrate generation (such as inhibiting nucleation, slowing the growth rate of crystals, preventing crystal aggregation and the like). The former method is commonly used during subsea oil and gas pipeline installation by adding sufficient 40 wt% ethylene glycol (MEG) to avoid hydrate formation. However, the viscosity of the simple MEG is too low to meet the requirements of pipeline transportation and installation.
Disclosure of Invention
The invention mainly aims to overcome the defects in the prior art and provide the delayed crosslinking gel with the interpenetrating network structure and the preparation method thereof, and the gel has the characteristics of good temperature resistance, controllable delayed crosslinking, easy gel breaking and small damage; the preparation method is reasonable and simple, has low cost and is suitable for large-scale marine petroleum pipeline installation and application.
The purpose of the invention is realized by the following technical scheme.
The invention relates to a delayed crosslinking gel with an interpenetrating network structure, which is characterized in that: the composition is prepared from the following components; the weight percentage of the first thickening agent is 0.1 to 10 percent, the weight percentage of the second thickening agent is 0.1 to 20 percent, the weight percentage of the cross-linking agent is 0.1 to 1 percent, the weight percentage of the PH regulator is 0.05 to 1 percent, the weight percentage of the bactericide is 0.01 to 1 percent, the weight percentage of the charge regulator is 0.1 to 1 percent, the weight percentage of the glycol is 10 to 40 percent, and the balance is water.
The delayed crosslinking gel with the interpenetrating network structure is characterized in that: the first thickening agent is one or a mixture of more of guar gum, fenugreek gum and modified guar gum; the modified guar gum is hydroxypropyl guar gum, carboxymethyl guar gum or hydroxypropyl carboxymethyl guar gum; the second thickening agent is polyvinyl alcohol; the cross-linking agent is formed by mixing a boron-containing cross-linking agent, glyoxal and water; wherein the weight percentage of the boron-containing cross-linking agent is 0.1 to 5 percent,the weight percentage of glyoxal is 0.1-10%, the rest is water; the boron-containing crosslinking agent is boric acid (H)3BO3) Borax, sodium metaborate (NaBO)2) Anhydrous sodium tetraborate (Na)2B4O7) Sodium tetraborate decahydrate (Na)2B4O7·10H2O), sodium tetraborate pentahydrate (Na)2B4O7·5H2O), disodium octaborate tetrahydrate (Na)2B8O13·4H2O) or a mixture of several of O); the pH regulator is one or a mixture of more of potassium carbonate, sodium carbonate and sodium hydroxide; the bactericide is one or a mixture of more of isothiazolinone, tetrakis (hydroxymethyl) phosphonium sulfate, dodecyl dimethyl benzyl ammonium chloride and dodecyl dimethyl benzyl ammonium bromide; the charge regulator is one or a mixture of more of sodium aminoacetate, sodium glycolate, ethanolamine, diethanolamine and triethanolamine; the water is deionized water.
The preparation method of the delayed crosslinking gel with the interpenetrating network structure is characterized by comprising the following steps of:
the first step is as follows: dissolving a first thickening agent in water at normal temperature and normal pressure, uniformly mixing at the rotating speed of 1000 +/-50 rpm, adding a pH regulator and a bactericide, and continuously stirring and uniformly mixing;
the second step is that: under normal temperature and normal pressure, increasing the rotating speed to 1500 +/-50 rpm, continuously adding the ethylene glycol aqueous solution, the charge regulator and the cross-linking agent solution into the mixed solution in the first step, and stirring and mixing uniformly; after the viscosity of the mixed solution reaches a preset value, injecting the mixed solution into a petroleum pipeline to be filled to form cross-linked gel containing a first thickening agent;
the third step: at normal temperature and normal pressure, opening valves at two ends of the pipeline, respectively pouring a mixture containing a second thickening agent, a cross-linking agent and water at two ends of the petroleum pipeline, and closing the valves at two sides of the pipeline; standing for 20 +/-5 hours to enable the gel formed by the second thickening agent to permeate into the first thickening agent crosslinked gel which is poured into the petroleum pipeline to form the delayed crosslinked gel with the interpenetrating network structure.
The preparation method of the delayed crosslinking gel with the interpenetrating network structure is characterized by comprising the following steps: the viscosity of the mixed solution in the second step is 10000 +/-100 mPaS.
The preparation method of the delayed crosslinking gel with the interpenetrating network structure is characterized by comprising the following steps: the delayed crosslinking gel with the interpenetrating network structure is prepared from the following components; the weight percentage of the first thickening agent is 0.1 to 10 percent, the weight percentage of the second thickening agent is 0.1 to 20 percent, the weight percentage of the cross-linking agent is 0.1 to 1 percent, the weight percentage of the PH regulator is 0.05 to 1 percent, the weight percentage of the bactericide is 0.01 to 1 percent, the weight percentage of the charge regulator is 0.1 to 1 percent, the weight percentage of the glycol is 10 to 40 percent, and the balance is water.
The preparation method of the delayed crosslinking gel with the interpenetrating network structure is characterized by comprising the following steps: the first thickening agent is one or a mixture of more of guar gum, fenugreek gum and modified guar gum; the modified guar gum is hydroxypropyl guar gum, carboxymethyl guar gum or hydroxypropyl carboxymethyl guar gum; the second thickening agent is polyvinyl alcohol; the cross-linking agent is formed by mixing a boron-containing cross-linking agent, glyoxal and water; wherein the weight percentage of the boron-containing cross-linking agent is 0.1 to 5 percent, the weight percentage of the glyoxal is 0.1 to 10 percent, and the balance is water; the boron-containing crosslinking agent is boric acid (H)3BO3) Borax, sodium metaborate (NaBO)2) Anhydrous sodium tetraborate (Na)2B4O7) Sodium tetraborate decahydrate (Na)2B4O7·10H2O), sodium tetraborate pentahydrate (Na)2B4O7·5H2O), disodium octaborate tetrahydrate (Na)2B8O13·4H2O) or a mixture of several of O); the pH regulator is one or a mixture of more of potassium carbonate, sodium carbonate and sodium hydroxide; the bactericide is one or a mixture of more of isothiazolinone, tetrakis (hydroxymethyl) phosphonium sulfate, dodecyl dimethyl benzyl ammonium chloride and dodecyl dimethyl benzyl ammonium bromide; the charge regulator is one or a mixture of more of sodium aminoacetate, sodium hydroxyacetate, ethanolamine, diethanolamine and triethanolamineAn agent; the water is deionized water.
The delayed crosslinking gel with the interpenetrating network structure and the preparation method thereof have the beneficial effects that: the delayed crosslinking gel with the interpenetrating network structure has the characteristics of adjustable crosslinking time, excellent chemical stability, controllable delayed crosslinking, easy gel breaking and small damage. The preparation method is reasonable and simple, has low cost and is suitable for large-scale marine petroleum pipeline installation and application.
Detailed Description
The invention relates to a delayed crosslinking gel with an interpenetrating network structure, which is prepared from the following components; the weight percentage of the first thickening agent is 0.1 to 10 percent, the weight percentage of the second thickening agent is 0.1 to 20 percent, the weight percentage of the cross-linking agent is 0.1 to 1 percent, the weight percentage of the PH regulator is 0.05 to 1 percent, the weight percentage of the bactericide is 0.01 to 1 percent, the weight percentage of the charge regulator is 0.1 to 1 percent, the weight percentage of the glycol is 10 to 40 percent, and the balance is water. Wherein the first thickening agent is one or a mixture of more of guar gum, fenugreek gum and modified guar gum; the modified guar gum is hydroxypropyl guar gum, carboxymethyl guar gum or hydroxypropyl carboxymethyl guar gum; the second thickener is polyvinyl alcohol; the cross-linking agent is formed by mixing a boron-containing cross-linking agent, glyoxal and water; wherein the weight percentage of the boron-containing cross-linking agent is 0.1 to 5 percent, the weight percentage of the glyoxal is 0.1 to 10 percent, and the balance is water; the boron-containing crosslinking agent is boric acid (H)3BO3) Borax, sodium metaborate (NaBO)2) Anhydrous sodium tetraborate (Na)2B4O7) Sodium tetraborate decahydrate (Na)2B4O7·10H2O), sodium tetraborate pentahydrate (Na)2B4O7·5H2O), disodium octaborate tetrahydrate (Na)2B8O13·4H2O) or a mixture of several of O); the pH regulator is one or a mixture of potassium carbonate, sodium carbonate and sodium hydroxide; the bactericide is one or a mixture of more of isothiazolinone, tetrakis (hydroxymethyl) phosphonium sulfate, dodecyl dimethyl benzyl ammonium chloride and dodecyl dimethyl benzyl ammonium bromide; the charge-regulating agent being an amino groupOne or a mixture of more of sodium acetate, sodium glycolate, ethanolamine, diethanolamine and triethanolamine; the water is deionized water.
The invention relates to a preparation method of delayed crosslinking gel with an interpenetrating network structure, which comprises the following steps:
the first step is as follows: dissolving a first thickening agent in water at normal temperature and normal pressure, uniformly mixing at the rotating speed of 1000 +/-50 rpm, adding a pH regulator and a bactericide, and continuously stirring and uniformly mixing;
the second step is that: under normal temperature and normal pressure, increasing the rotating speed to 1500 +/-50 rpm, continuously adding the ethylene glycol aqueous solution, the charge regulator and the cross-linking agent solution into the mixed solution in the first step, and stirring and mixing uniformly; after the viscosity of the mixed solution reaches a preset value, injecting the mixed solution into a petroleum pipeline to be filled to form cross-linked gel containing a first thickening agent;
the third step: at normal temperature and normal pressure, opening valves at two ends of the pipeline, respectively pouring a mixture containing a second thickening agent, a cross-linking agent and water at two ends of the petroleum pipeline, and closing the valves at two sides of the pipeline; standing for 20 +/-5 hours to enable the gel formed by the second thickening agent to permeate into the first thickening agent crosslinked gel which is poured into the petroleum pipeline to form the delayed crosslinked gel with the interpenetrating network structure.
The invention relates to a preparation method of delayed crosslinking gel with an interpenetrating network structure, wherein the preparation method comprises the following steps: the viscosity of the mixed solution in the second step is 10000 +/-100 mPas; the delayed crosslinking gel with the interpenetrating network structure is prepared from the following components; 0.1 to 10 percent of first thickening agent, 0.1 to 20 percent of second thickening agent, 0.1 to 1 percent of cross-linking agent, 0.05 to 1 percent of PH regulator, 0.01 to 1 percent of bactericide, 0.1 to 1 percent of charge regulator, 10 to 40 percent of glycol and the balance of water; the first thickening agent is one or a mixture of more of guar gum, fenugreek gum and modified guar gum; the modified guar gum is hydroxypropyl guar gum, carboxymethyl guar gum or hydroxypropyl carboxymethyl guar gum; the second thickening agent is polyvinyl alcohol; the cross-linking agent is composed of boron-containing cross-linking agent and BDialdehyde and water are mixed; wherein the weight percentage of the boron-containing cross-linking agent is 0.1 to 5 percent, the weight percentage of the glyoxal is 0.1 to 10 percent, and the balance is water; the boron-containing crosslinking agent is boric acid (H)3BO3) Borax, sodium metaborate (NaBO)2) Anhydrous sodium tetraborate (Na)2B4O7) Sodium tetraborate decahydrate (Na)2B4O7·10H2O), sodium tetraborate pentahydrate (Na)2B4O7·5H2O), disodium octaborate tetrahydrate (Na)2B8O13·4H2O) or a mixture of several of O); the pH regulator is one or a mixture of more of potassium carbonate, sodium carbonate and sodium hydroxide; the bactericide is one or a mixture of more of isothiazolinone, tetrakis (hydroxymethyl) phosphonium sulfate, dodecyl dimethyl benzyl ammonium chloride and dodecyl dimethyl benzyl ammonium bromide; the charge regulator is one or a mixture of more of sodium aminoacetate, sodium glycolate, ethanolamine, diethanolamine and triethanolamine; the water is deionized water.
Example (b):
the preparation method of the delayed crosslinking gel with the interpenetrating network structure comprises the following steps:
firstly, dissolving guar gum in deionized water at 25 ℃ under normal pressure, stirring for 30min at the rotating speed of 1000rpm, and uniformly mixing to obtain a first thickening agent with the weight percentage of 10%; then adding 1 weight percent of potassium carbonate (pH regulator) into the first thickening agent, and regulating the pH value to be 8-10; then adding 1 percent by weight of tetrakis hydroxymethyl phosphonium sulfate (bactericide), stirring for 10min, and uniformly mixing to obtain a light yellow transparent viscous liquid;
secondly, increasing the rotating speed to 1500rpm at the temperature of 25 ℃ and normal pressure, adding 40 weight percent of ethylene glycol, 1 weight percent of charge regulator and 0.5 weight percent of cross-linking agent into the yellowish transparent viscous liquid obtained in the first step, and stirring and mixing uniformly; when the viscosity of the solution reaches 10000mPas (rotating speed 6rpm, 3# rotor), injecting the solution into a 6-inch pipeline to be filled, and closing valves at two ends of the pipeline; wherein, the charge regulator with the weight percentage of 1 percent is the mixed solution of sodium glycolate and triethanolamine; the cross-linking agent with the weight percentage of 0.5 percent is a mixed solution of glyoxal, sodium tetraborate decahydrate and water;
thirdly, at the temperature of 25 ℃ and normal pressure, opening valves at two ends of the pipeline, and injecting a second thickening agent with the weight percentage of 20 percent and a crosslinking agent with the weight percentage of 0.5 percent into the two ends of the pipeline by using a gel injection pump; wherein the second thickening agent is polyvinyl alcohol; the cross-linking agent is a mixed solution of glyoxal, sodium tetraborate decahydrate and water; closing valves at two sides of the pipeline; and standing for 24 hours to enable the polyvinyl alcohol to permeate into the guar cross-linked gel network to form the delayed cross-linked gel with the interpenetrating network structure.
The gel has a mutually-penetrated crosslinking network, can effectively improve the stability and temperature resistance of the gel through the synergistic effect of the high-molecular chain segments, and has a good use effect.
The content that is not described in this embodiment is the prior art, and therefore, the description thereof is omitted.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and all simple modifications, equivalent variations and modifications made to the above embodiments according to the technical spirit of the present invention are within the scope of the present invention.
Claims (6)
1. A delayed crosslinked gel having an interpenetrating network structure, characterized by: the composition is prepared from the following components; the weight percentage of the first thickening agent is 0.1 to 10 percent, the weight percentage of the second thickening agent is 0.1 to 20 percent, the weight percentage of the cross-linking agent is 0.1 to 1 percent, the weight percentage of the PH regulator is 0.05 to 1 percent, the weight percentage of the bactericide is 0.01 to 1 percent, the weight percentage of the charge regulator is 0.1 to 1 percent, the weight percentage of the glycol is 10 to 40 percent, and the balance is water.
2. The delayed crosslinked gel with interpenetrating network structure of claim 1, characterized in that: the first thickening agent is one or a mixture of more of guar gum, fenugreek gum and modified guar gum; the modified guar gum is hydroxypropyl guar gum, carboxymethyl guar gum or hydroxypropyl carboxymethyl guar gum;
the second thickening agent is polyvinyl alcohol;
the cross-linking agent is formed by mixing a boron-containing cross-linking agent, glyoxal and water; wherein the weight percentage of the boron-containing cross-linking agent is 0.1 to 5 percent, the weight percentage of the glyoxal is 0.1 to 10 percent, and the balance is water; the boron-containing crosslinking agent is boric acid (H)3BO3) Borax, sodium metaborate (NaBO)2) Anhydrous sodium tetraborate (Na)2B4O7) Sodium tetraborate decahydrate (Na)2B4O7·10H2O), sodium tetraborate pentahydrate (Na)2B4O7·5H2O), disodium octaborate tetrahydrate (Na)2B8O13·4H2O) or a mixture of several of O);
the pH regulator is one or a mixture of more of potassium carbonate, sodium carbonate and sodium hydroxide;
the bactericide is one or a mixture of more of isothiazolinone, tetrakis (hydroxymethyl) phosphonium sulfate, dodecyl dimethyl benzyl ammonium chloride and dodecyl dimethyl benzyl ammonium bromide;
the charge regulator is one or a mixture of more of sodium aminoacetate, sodium glycolate, ethanolamine, diethanolamine and triethanolamine;
the water is deionized water.
3. A method for preparing a delayed crosslinked gel having an interpenetrating network structure according to claim 1, comprising the steps of:
the first step is as follows: dissolving a first thickening agent in water at normal temperature and normal pressure, uniformly mixing at the rotating speed of 1000 +/-50 rpm, adding a pH regulator and a bactericide, and continuously stirring and uniformly mixing;
the second step is that: under normal temperature and normal pressure, increasing the rotating speed to 1500 +/-50 rpm, continuously adding the ethylene glycol aqueous solution, the charge regulator and the cross-linking agent solution into the mixed solution in the first step, and stirring and mixing uniformly; after the viscosity of the mixed solution reaches a preset value, injecting the mixed solution into a petroleum pipeline to be filled to form cross-linked gel containing a first thickening agent;
the third step: at normal temperature and normal pressure, opening valves at two ends of the pipeline, respectively pouring a mixture containing a second thickening agent, a cross-linking agent and water at two ends of the petroleum pipeline, and closing the valves at two sides of the pipeline; standing for 20 +/-5 hours to enable the gel formed by the second thickening agent to permeate into the first thickening agent crosslinked gel which is poured into the petroleum pipeline to form the delayed crosslinked gel with the interpenetrating network structure.
4. The method for preparing a delayed crosslinked gel having an interpenetrating network structure according to claim 3, wherein: the viscosity of the mixed solution in the second step is 10000 +/-100 mPaS.
5. The method for preparing a delayed crosslinked gel having an interpenetrating network structure according to claim 3, wherein: the delayed crosslinking gel with the interpenetrating network structure is prepared from the following components; the weight percentage of the first thickening agent is 0.1 to 10 percent, the weight percentage of the second thickening agent is 0.1 to 20 percent, the weight percentage of the cross-linking agent is 0.1 to 1 percent, the weight percentage of the PH regulator is 0.05 to 1 percent, the weight percentage of the bactericide is 0.01 to 1 percent, the weight percentage of the charge regulator is 0.1 to 1 percent, the weight percentage of the glycol is 10 to 40 percent, and the balance is water.
6. The method for preparing a delayed crosslinked gel having an interpenetrating network structure according to claim 5, wherein: the first thickening agent is one or a mixture of more of guar gum, fenugreek gum and modified guar gum; the modified guar gum is hydroxypropyl guar gum, carboxymethyl guar gum or hydroxypropyl carboxymethyl guar gum;
the second thickening agent is polyvinyl alcohol;
the cross-linking agent is formed by mixing a boron-containing cross-linking agent, glyoxal and water; wherein the weight percentage of the boron-containing cross-linking agent is 0.1To 5%, glyoxal in an amount of 0.1 to 10% by weight, and water in balance; the boron-containing crosslinking agent is boric acid (H)3BO3) Borax, sodium metaborate (NaBO)2) Anhydrous sodium tetraborate (Na)2B4O7) Sodium tetraborate decahydrate (Na)2B4O7·10H2O), sodium tetraborate pentahydrate (Na)2B4O7·5H2O), disodium octaborate tetrahydrate (Na)2B8O13·4H2O) or a mixture of several of O);
the pH regulator is one or a mixture of more of potassium carbonate, sodium carbonate and sodium hydroxide;
the bactericide is one or a mixture of more of isothiazolinone, tetrakis (hydroxymethyl) phosphonium sulfate, dodecyl dimethyl benzyl ammonium chloride and dodecyl dimethyl benzyl ammonium bromide;
the charge regulator is one or a mixture of more of sodium aminoacetate, sodium glycolate, ethanolamine, diethanolamine and triethanolamine;
the water is deionized water.
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| CN112592619A (en) * | 2020-12-22 | 2021-04-02 | 闫明亮 | Antibacterial and mildew-proof putty powder and preparation method thereof |
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| CN1524920A (en) * | 2003-02-28 | 2004-09-01 | 中国石油天然气股份有限公司 | Organic boron delayed crosslinking plant gum fracturing fluid |
| US20110005756A1 (en) * | 2005-12-09 | 2011-01-13 | Clearwater International, Llc | Use of zeta potential modifiers to decrease the residual oil saturation |
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