CN108441203B - Salt-resistant organic boron chromium crosslinking agent, and preparation method and application thereof - Google Patents
Salt-resistant organic boron chromium crosslinking agent, and preparation method and application thereof Download PDFInfo
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- CN108441203B CN108441203B CN201810312593.3A CN201810312593A CN108441203B CN 108441203 B CN108441203 B CN 108441203B CN 201810312593 A CN201810312593 A CN 201810312593A CN 108441203 B CN108441203 B CN 108441203B
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/66—Compositions based on water or polar solvents
- C09K8/68—Compositions based on water or polar solvents containing organic compounds
- C09K8/685—Compositions based on water or polar solvents containing organic compounds containing cross-linking agents
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/66—Compositions based on water or polar solvents
- C09K8/665—Compositions based on water or polar solvents containing inorganic compounds
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Abstract
The invention discloses a salt-tolerant organic boron chromium crosslinking agent, a preparation method and application thereof, and relates to the technical field of crosslinking agents. The salt-resistant organic boron chromium crosslinking agent comprises, by weight, 10-40 parts of borax, 5-30 parts of glycerol, 5-15 parts of polyhydroxy compound, 1-10 parts of chromium-containing compound and 5-80 parts of water. The addition of the chromium-containing compound can obviously improve the salt resistance of the cross-linking agent, greatly reduce the requirement on water quality during the preparation of the guanidine gum fracturing fluid and achieve the aim of saving water resources. The preparation method of the salt-resistant organic boron chromium crosslinking agent has the advantages of mild synthesis conditions, simple preparation process and convenience for large-scale application. The jelly glue prepared by the salt-tolerant organic boron chromium crosslinking agent obtained by the formula and the preparation method has the viscosity of more than 50mPa & s after shearing for 2 hours under the condition that the calcium chloride content is 1%, and can meet the construction operation requirement.
Description
Technical Field
The invention relates to the technical field of cross-linking agents, and particularly relates to a salt-resistant organic boron chromium cross-linking agent, and a preparation method and application thereof.
Background
Hydraulic fracturing is an important measure for the current oil field reservoir reconstruction, the used thickening agent is hydroxypropyl guar gum, and the used crosslinking agent is a boron-containing compound.
But has the following disadvantages: the guanidine gum fracturing system which singly takes the boron-containing compound as the cross-linking agent has poor divalent salt resistance, clear water with low mineralization degree is required to prepare fracturing fluid, and the required amount of the clear water is large. Therefore, the cross-linking agent for the salt-tolerant guanidine gum fracturing fluid can save a large amount of water resources and bring great convenience to hydraulic fracturing operation in water-deficient areas.
Disclosure of Invention
The invention aims to provide a salt-tolerant organic boron chromium crosslinking agent, which aims to improve the salt tolerance of the crosslinking agent, greatly reduce the dependence of construction operation on clear water and achieve the aim of saving water.
The invention also aims to provide a preparation method of the salt-resistant organic boron chromium crosslinking agent, which is simple and feasible and is suitable for industrial application.
The third purpose of the invention is to provide the application of the salt-resistant organic boron chromium crosslinking agent in preparing a guanidine gum fracturing fluid.
The technical problem to be solved by the invention is realized by adopting the following technical scheme.
The invention provides a salt-tolerant organic boron chromium crosslinking agent, which comprises, by weight, 10-40 parts of borax, 5-30 parts of glycerol, 5-15 parts of polyhydroxy compound, 1-10 parts of chromium-containing compound and 5-80 parts of water.
The invention also provides a preparation method of the salt-resistant organic boron chromium crosslinking agent, which comprises the following steps:
stirring and mixing raw materials of a cross-linking agent, wherein the raw materials of the cross-linking agent comprise 10-40 parts of borax, 5-30 parts of glycerol, 5-15 parts of polyhydroxy compound, 1-10 parts of chromium-containing compound and 5-80 parts of water.
The invention also provides the application of the salt-resistant organic boron chromium crosslinking agent in preparing the guanidine gum fracturing fluid; preferably, the guar is hydroxypropyl guar.
The embodiment of the invention provides a salt-resistant organic boron chromium crosslinking agent, which has the beneficial effects that: the cross-linking agent is prepared from borax, glycerol, a polyhydroxy compound, a chromium-containing compound and water according to a certain proportion, and the inventor finds that the addition of the chromium-containing compound can obviously improve the salt resistance of the cross-linking agent, greatly reduces the requirement on water quality during the preparation of the guanidine gum fracturing fluid, and achieves the purpose of saving water resources. The preparation method of the salt-tolerant organic boron chromium crosslinking agent provided by the invention has the advantages of mild synthesis conditions, simple preparation process and convenience for large-scale application. The jelly glue prepared by the salt-tolerant organic boron chromium crosslinking agent obtained by the formula and the preparation method has the viscosity of more than 50mPa & s after shearing for 2 hours under the condition that the calcium chloride content is 1%, and can meet the construction operation requirement.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The salt-tolerant organic boron chromium crosslinking agent provided by the embodiment of the invention, and a preparation method and application thereof are provided below.
According to the salt-tolerant organic boron chromium crosslinking agent provided by the embodiment of the invention, the raw materials of the crosslinking agent comprise, by weight, 10-40 parts of borax, 5-30 parts of glycerol, 5-15 parts of polyhydroxy compound, 1-10 parts of chromium-containing compound and 5-80 parts of water.
It should be noted that in the formula of the salt-tolerant organic boron chromium crosslinking agent provided by the embodiment of the invention, borax is a basic crosslinking raw material, and glycerol and a polyhydroxy compound can increase the solubility of borax, and the inventor finds that the addition of a chromium-containing compound can significantly improve the salt tolerance of the crosslinking agent, greatly reduces the requirement on water quality during the preparation of a guanidine gum fracturing fluid, and achieves the purpose of saving water resources.
The components in the formula of the salt-tolerant organoboron-chromium crosslinking agent provided by the embodiment of the invention need to be controlled within the above range so as to ensure the crosslinking performance and salt tolerance of the crosslinking agent. If the dosage of the borax is too large, the salt resistance is not strong, and the dosage proportion of the borax and the chromium-containing compound needs to be controlled within the range, so that the cross-linking performance and the salt resistance of the product can be ensured. The amount of glycerin and polyol should not be too large to affect the performance of the product.
Preferably, the raw materials of the cross-linking agent comprise 30-40 parts of borax, 15-20 parts of glycerol, 5-13 parts of polyhydroxy compound, 2-5 parts of chromium-containing compound and 20-50 parts of water. The components in the formula of the salt-resistant organic boron chromium crosslinking agent are controlled within the proportion range, and the prepared crosslinking agent can adapt to the environment with high salt content, can still reduce the water consumption and has good application value.
Specifically, the polyhydroxy compound is selected from one or more of lactose, sodium gluconate, sodium glucoheptonate and sorbitol, and the chromium-containing compound is chromium trichloride. The inventor finds that the salt resistance of borax as a cross-linking agent can be obviously improved when the added chromium-containing compound is chromium trichloride, and the polyhydroxy compound can play a role in enhancing the complexing effect and improving the dissolving performance of borax.
The embodiment of the invention also provides a preparation method of the salt-tolerant organic boron chromium crosslinking agent, which comprises the following steps: the raw materials of the cross-linking agent are stirred and mixed, the method is simple and easy to implement and is suitable for industrial application, and the raw materials of the cross-linking agent comprise 10-40 parts of borax, 5-30 parts of glycerol, 5-15 parts of polyhydroxy compound, 1-10 parts of chromium-containing compound and 5-80 parts of water.
Preferably, the temperature in the process of mixing the raw materials of the cross-linking agent is 70-90 ℃, and the stirring is carried out for 2-4 h. In the preparation process of the cross-linking agent, the mixing process of the raw materials is controlled to be about 80 ℃, and the reaction time is controlled to be about 3 hours, so that a good complexing effect can be achieved, and a uniform cross-linking agent product can be obtained. Side reactions are easily caused when the temperature is too high, and products with excellent and uniform performance are not easily obtained when the temperature is too low.
Therefore, the preparation method of the salt-tolerant organic boron chromium crosslinking agent provided by the embodiment of the invention has the advantages of mild synthesis conditions, simple preparation process and convenience for large-scale application.
The inventor finds that the jelly glue prepared by the salt-tolerant organic boron chromium crosslinking agent obtained by the formula and the preparation method can meet the construction operation requirement, and the viscosity is more than 50mPa & s after shearing for 2 hours under the condition that the calcium chloride content is 1%. Therefore, the salt-resistant organic boron chromium crosslinking agent can be applied to preparation of the guanidine gum fracturing fluid, wherein the guanidine gum is hydroxypropyl guanidine gum generally.
In order to ensure the performance of the guanidine gum fracturing fluid and adapt to the condition of high mineralized water quality, in the guanidine gum fracturing fluid, the mass fraction of the salt-tolerant organic boron chromium crosslinking agent is 0.1-0.3%, and the mass fraction of the divalent salt is less than 1%.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment provides a salt-tolerant organic boron chromium crosslinking agent, which comprises the following raw materials, by weight, 10 parts of borax, 5 parts of glycerol, 5 parts of polyhydroxy compound, 1 part of chromium trichloride and 79 parts of water;
wherein, the polyhydroxy compound comprises 2 parts of lactose and 3 parts of sodium gluconate.
The embodiment also provides a preparation method of the salt-tolerant organic boron chromium crosslinking agent, which comprises the following steps:
the above raw materials were added to a round bottom flask equipped with a magnetic stirrer and heated to 70 ℃ with stirring for 4h reaction.
Example 2
The embodiment provides a salt-tolerant organic boron chromium crosslinking agent, which comprises, by weight, 40 parts of borax, 30 parts of glycerol, 15 parts of polyhydroxy compound, 10 parts of chromium trichloride and 5 parts of water;
wherein the polyhydroxy compound comprises 10 parts of sodium glucoheptonate and 10 parts of sorbitol.
The embodiment also provides a preparation method of the salt-tolerant organic boron chromium crosslinking agent, which comprises the following steps:
the above raw materials were added to a round bottom flask equipped with a magnetic stirrer and heated to 90 ℃ with stirring for 2 h.
Example 3
The embodiment provides a salt-tolerant organic boron chromium crosslinking agent, which comprises, by weight, 30 parts of borax, 15 parts of glycerol, 5 parts of polyhydroxy compound, 2 parts of chromium trichloride and 48 parts of water;
wherein the polyhydroxy compound comprises 3 parts of sodium gluconate and 2 parts of sodium glucoheptonate.
The embodiment also provides a preparation method of the salt-tolerant organic boron chromium crosslinking agent, which comprises the following steps:
the above raw materials were added to a round bottom flask equipped with a magnetic stirrer and heated to 80 ℃ with stirring to react for 3 h.
Example 4
The embodiment provides a salt-tolerant organic boron chromium crosslinking agent, which comprises, by weight, 40 parts of borax, 20 parts of glycerol, 13 parts of polyhydroxy compound, 5 parts of chromium trichloride and 22 parts of water;
wherein the polyhydroxy compound comprises 8 parts of sodium gluconate and 7 parts of sodium glucoheptonate.
The embodiment also provides a preparation method of the salt-tolerant organic boron chromium crosslinking agent, which comprises the following steps:
the above raw materials were added to a round bottom flask equipped with a magnetic stirrer and heated to 80 ℃ with stirring to react for 3 h.
Comparative example 1
The difference from example 4 is that: the formula of the salt-resistant organoboron-chromium crosslinking agent does not comprise chromium trichloride.
Comparative example 2
The difference from example 4 is that: the chromium trichloride in the formula of the salt-resistant organic boron chromium crosslinking agent is replaced by zirconium tetrachloride.
Test example 1
The cross-linking agents prepared in examples 1-4 and comparative examples 1-3 were used in the preparation of fracturing fluids and the properties of the fracturing fluids were tested.
The test method comprises the following steps: preparing 0.4% of hydroxypropyl guar gum by using clear water, and adding calcium chloride with different mass fractions to prepare base solution; taking 100ml of base solution, adding 0.15ml of cross-linking agent for salt-resistant guanidine gum fracturing fluid and 1.5ml of sodium hydroxide with the mass fraction of 1%, and stirring to obtain jelly; then, the gel 170S is measured according to the stipulation of SY/T6216 'test method for the performance of the crosslinking agent of the fracturing fluid', the test temperature is 100 DEG C-1The viscosity after 2h of shearing is shown in Table 1.
TABLE 1 fracturing fluid crosslinker Performance test results
As can be seen from Table 1, the salt tolerance of the fracturing fluid obtained when the cross-linking agent obtained by the cross-linking agent formula and the preparation method provided by the embodiments 1-4 of the invention is used for preparing the fracturing fluid is excellent, and when the addition amount of calcium chloride is 0.5%, the viscosity corresponding to the cross-linking agent in the embodiments 1-4 is more than 110mPa & s and is obviously higher than that in the comparative example 1; similarly, the crosslinking agents of examples 1 to 4 exhibited significantly higher viscosities than those of comparative example 1 at a calcium chloride addition of 1% and above 80 mPas.
In addition, the test results of examples 1-4 are not very different from the test results of comparative example 2, the salt tolerance of the cross-linking agent in examples 1-4 of the invention is stronger, and the advantage is more obvious especially when the addition amount of calcium chloride is 1%.
In conclusion, the invention provides a salt-tolerant organic boron chromium crosslinking agent, which is prepared from borax, glycerol, polyhydroxy compound, chromium-containing compound and water in a certain proportion.
The preparation method of the salt-tolerant organic boron chromium crosslinking agent provided by the invention has the advantages of mild synthesis conditions, simple preparation process and convenience for large-scale application.
The jelly glue prepared by the salt-tolerant organic boron chromium crosslinking agent obtained by the formula and the preparation method has the viscosity of more than 50mPa & s after shearing for 2 hours under the condition that the calcium chloride content is 1%, and can meet the construction operation requirement.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (9)
1. A salt-tolerant organic boron chromium crosslinking agent is used for hydroxypropyl guar gum fracturing fluid and is characterized in that raw materials of the crosslinking agent comprise 10-40 parts of borax, 5-30 parts of glycerol, 5-15 parts of polyhydroxy compound, 1-10 parts of chromium-containing compound and 5-80 parts of water in parts by weight;
the chromium-containing compound is chromium trichloride.
2. The salt-tolerant organoboron chromium crosslinking agent of claim 1, wherein the raw materials of the crosslinking agent comprise 30-40 parts of borax, 15-20 parts of glycerol, 5-13 parts of polyhydroxy compound, 2-5 parts of chromium-containing compound and 20-50 parts of water.
3. The salt-tolerant organoboron chromium crosslinker of claim 1 or 2, characterized in that the polyol is selected from one or more of lactose, sodium gluconate, sodium glucoheptonate and sorbitol.
4. The method of preparing the salt-tolerant organoboron chromium crosslinker of any of claims 1 to 3, comprising the steps of:
the raw materials of the cross-linking agent are stirred and mixed.
5. The method for preparing the salt-tolerant organoboron chromium crosslinking agent according to claim 4, wherein the temperature during the mixing of the raw materials of the crosslinking agent is 70-90 ℃.
6. The method for preparing the salt-tolerant organoboron-chromium crosslinking agent of claim 5, wherein the raw materials of the crosslinking agent are stirred for 2-4h during the mixing process.
7. Use of the salt-tolerant organoboron chromium crosslinker of any of claims 1 to 3 in the preparation of a guanidine gum fracturing fluid.
8. The use of claim 7, wherein the salt-tolerant organoboron-chromium crosslinker is present in the guanidine gum fracturing fluid at a mass fraction of 0.1% to 0.3%.
9. The use according to claim 8, wherein the mass fraction of divalent salt in the guanidine gum fracturing fluid is less than 1%.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102618248A (en) * | 2012-03-02 | 2012-08-01 | 陕西延长石油(集团)有限责任公司研究院 | High-chelating-degree liquid state boron cross-linking agent for gugnidine glue fracturing fluid |
| CN103965857A (en) * | 2013-01-30 | 2014-08-06 | 中国石油天然气集团公司 | Preparation method of High-temperature water base fracturing fluid |
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| EP2984134A4 (en) * | 2013-04-10 | 2016-12-21 | Ecolab Usa Inc | Choline-based crosslinker compositions for fracturing fluids |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102618248A (en) * | 2012-03-02 | 2012-08-01 | 陕西延长石油(集团)有限责任公司研究院 | High-chelating-degree liquid state boron cross-linking agent for gugnidine glue fracturing fluid |
| CN103965857A (en) * | 2013-01-30 | 2014-08-06 | 中国石油天然气集团公司 | Preparation method of High-temperature water base fracturing fluid |
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