[go: up one dir, main page]

CN103865507A - Preparation method and application of micro-molecular anti-swelling shrinkage agent - Google Patents

Preparation method and application of micro-molecular anti-swelling shrinkage agent Download PDF

Info

Publication number
CN103865507A
CN103865507A CN201410067571.7A CN201410067571A CN103865507A CN 103865507 A CN103865507 A CN 103865507A CN 201410067571 A CN201410067571 A CN 201410067571A CN 103865507 A CN103865507 A CN 103865507A
Authority
CN
China
Prior art keywords
amine
mixture
solvent
carboxylic acid
small molecule
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201410067571.7A
Other languages
Chinese (zh)
Inventor
陈刚
张洁
蔡丹
张黎
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xian Shiyou University
Original Assignee
Xian Shiyou University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xian Shiyou University filed Critical Xian Shiyou University
Priority to CN201410067571.7A priority Critical patent/CN103865507A/en
Publication of CN103865507A publication Critical patent/CN103865507A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/607—Compositions for stimulating production by acting on the underground formation specially adapted for clay formations
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/12—Swell inhibition, i.e. using additives to drilling or well treatment fluids for inhibiting clay or shale swelling or disintegrating

Landscapes

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

Abstract

The invention discloses a preparation method and application of a micro-molecular anti-swelling shrinkage agent. The preparation method of the micro-molecular anti-swelling shrinkage agent comprises the steps of dissolving amine into a solvent in a reaction kettle, uniformly stirring, adding carboxylic acid into the solution while stirring to obtain a mixture, heating the mixture until the mixture is completely dissolved, steaming the solvent in the mixture, and cooling to room temperature; transferring the mixture into a mortar, adding potassium chloride, and uniformly grinding the mixture and added potassium chloride to obtain the micro-molecular anti-swelling shrinkage agent. During application, the dosage of the micro-molecular anti-swelling shrinkage agent takes 0.1-2.0% of the mass of oil field working liquid; the anti-swelling rate of the micro-molecular anti-swelling shrinkage agent to clay is 50-80%; the swelling shrinkage ratio of the micro-molecular anti-swelling shrinkage agent is more than 20%. The micro-molecular anti-swelling shrinkage agent disclosed by the invention is small in molecular weight, good in inhibition performance and environment-friendly.

Description

The preparation and application that the anti-swollen contracting of a kind of small molecules is swollen dose
Technical field
The present invention relates to anti-swollen dose of preparing technical field of swollen contracting, be specifically related to the preparation and application of swollen dose of the anti-swollen contracting of a kind of small molecules.
Background technology
The main component of mud shale is clay mineral, layer mineral---the montmorillonite that wherein the superfine hydrous alumino silicates of particle forms, in its structure, reactive force is between layers weak Van der Waals force, with water base oilfield working fluids interaction process in easily water-swelling.The Complicated Fault Block Oilfield of low permeability and high pressure, clay mineral content is high, meets water and easily expands, migrates, and causes permeability plugging, and water injection pressure rises, and oil recovery ratio declines.The injuries that adopt the method for water filling initial stage interpolation clay stabilizer to slow down clay class mineral pair reservoir in the actual production of oil field at present more.For the situation of hydration swelling of clay mineral, traditional clay stabilizer is that expansion-resisting agent is very little to the restitution of reservoir penetrating power.For this situation, mainly take at present acidification to dispel block measure to remove reservoir pollution, but conventional souring method has, treatment radius is little, validity period is short, acidizing fluid itself injures the defects such as large to oil reservoir.
Contract swollen dose and have the anti-swollen function of traditional clay stabilizer concurrently, can make the clay dehydration of hydration swelling contract swollen, recover the penetrating power of reservoir.The research that at present domestic relevant contracting is swollen dose is less, and basic is all relative molecular mass at 1000 ~ 100000 organic cationic polymer.But because its molecular weight is larger, on the one hand molecular weight is excessive has limited its application at low permeability oil field, can only be adsorbed on the other hand clay surface, for the strong clay of swelling property, the inhibition of polyamine class shale clay swelling inhibitor is unsatisfactory.In addition, part polyamine class shale clay swelling inhibitor also exist toxicity large, with the problems such as anionic treatments agent compatibleness is poor.
Summary of the invention
In order to overcome the shortcoming of prior art, the object of the present invention is to provide the preparation and application of swollen dose of the anti-swollen contracting of a kind of small molecules, small molecules prevents that the molecular weight of swollen dose of swollen contracting is little, rejection good, environmental friendliness.
In order to achieve the above object, the technical solution used in the present invention is:
The preparation that the anti-swollen contracting of small molecules is swollen dose, comprises the following steps:
The first step, in reactor, amine is dissolved in 5-30 solvent doubly, stir, described amine is thanomin, diethanolamine, trolamine, quadrol, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, five ethene hexamines of technical grade and above purity thereof and composition thereof, and described solvent is water of technical grade and above purity methyl alcohol, ethanol or the above purity of tap water and composition thereof;
Second step, under stirring to add in above-mentioned solution with amine in the amido functional group ratio carboxylic acid that is 1:1-5, described carboxylic acid is lactic acid, oxysuccinic acid, tartrate, citric acid, gluconic acid, L-glutamic acid of technical grade and above purity thereof and composition thereof;
The 3rd step, is heated to 30-100 DEG C by said mixture, all dissolves to it;
The 4th step, boils off solvent in said mixture, is cooled to room temperature;
The 5th step, is transferred to said mixture in mortar, and the Repone K that to add with amine and carboxylic acid total mass ratio be 5-0.5:1 grinds evenly, obtains swollen dose of the anti-swollen contracting of small molecules, and described Repone K is the product of technical grade and above purity thereof.
When application, the 0.1-2.0% that the anti-swollen dose of consumption of swollen contracting of small molecules is oilfield working fluids quality, its anti-swollen rate to clay is 50-80%, the swollen rate that contracts is greater than 20%.
Advantage of the present invention: repair mud stone bioactive molecule and clay mineral (montmorillonite, illite) generation physical-chemical reaction behind swollen dose of injection stratum of the anti-swollen contracting of small molecules, make clay lattice modification, make not expand after its chance water; The clay lattice having expanded, by discharging water molecules after chemical reaction modification, lattice dwindles.Bioactive molecule enters calmly pore space widely, reduce surface tension, eliminate the water blocking damage of large particle water, clean stratum, and make clay material and the former stratum mineral mortise of these modifications by multipoint adsorption effect, meet water injury thereby removed clay mineral, water lock, the injury that water-sensitive expands, migration causes stratum, reach step-down augmented injection, recover effective permeability, improve the outstanding effect of oil and gas development.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1
The preparation that the anti-swollen contracting of small molecules is swollen dose, comprises the following steps:
The first step is dissolved in amine in the solvent of 5 times in reactor, stirs, and described amine is technical grade diethanolamine, and described solvent is industrial grade benzenemethanol;
Second step, under stirring to add in above-mentioned solution with amine in the amido functional group ratio carboxylic acid that is 1:1, described carboxylic acid is the lactic acid of technical grade and above purity thereof;
The 3rd step, is heated to 30 DEG C by said mixture, all dissolves to it;
The 4th step, boils off solvent in said mixture, is cooled to room temperature;
The 5th step, is transferred to said mixture in mortar, and the Repone K that to add with amine and carboxylic acid total mass ratio be 5:1 grinds evenly, obtains swollen dose of the anti-swollen contracting of small molecules, and described Repone K is the product of technical grade and above purity thereof.
When application, the anti-swollen dose of consumption of swollen contracting of small molecules is 2.0% of oilfield working fluids quality, and its anti-swollen rate to clay is 68%, and the swollen rate that contracts is 21%.
Embodiment 2
The preparation that the anti-swollen contracting of small molecules is swollen dose, comprises the following steps:
The first step is dissolved in amine in the solvent of 8 times in reactor, stirs, and described amine is technical grade trolamine, and described solvent is chemical pure ethanol;
Second step, under stirring to add in above-mentioned solution with amine in the amido functional group ratio carboxylic acid that is 1:1, described carboxylic acid is technical grade tartrate;
The 3rd step, is heated to 40 DEG C by said mixture, all dissolves to it;
The 4th step, boils off solvent in said mixture, is cooled to room temperature;
The 5th step, is transferred to said mixture in mortar, and the Repone K that to add with amine and carboxylic acid total mass ratio be 3:1 grinds evenly, obtains swollen dose of the anti-swollen contracting of small molecules, and described Repone K is the product of technical grade and above purity thereof.
When application, the anti-swollen dose of consumption of swollen contracting of small molecules is 1.5% of oilfield working fluids quality, and its anti-swollen rate to clay is 59%, and the swollen rate that contracts is 26%.
Embodiment 3
The preparation that the anti-swollen contracting of small molecules is swollen dose, comprises the following steps:
The first step is dissolved in amine in the solvent of 15 times in reactor, stirs, and described amine is analytical pure diethylenetriamine, and described solvent is analytical pure methyl alcohol;
Second step, under stirring to add in above-mentioned solution with amine in the amido functional group ratio carboxylic acid that is 1:3, described carboxylic acid is chemical pure citric acid;
The 3rd step, is heated to 55 DEG C by said mixture, all dissolves to it;
The 4th step, boils off solvent in said mixture, is cooled to room temperature;
The 5th step, is transferred to said mixture in mortar, and the Repone K that to add with amine and carboxylic acid total mass ratio be 1:1 grinds evenly, obtains swollen dose of the anti-swollen contracting of small molecules, and described Repone K is technical grade product.
When application, the anti-swollen dose of consumption of swollen contracting of small molecules is 0.8% of oilfield working fluids quality, and its anti-swollen rate to clay is 76%, and the swollen rate that contracts is 25%.
Embodiment 4
The preparation that the anti-swollen contracting of small molecules is swollen dose, comprises the following steps:
The first step is dissolved in amine in the solvent of 20 times in reactor, stirs, and described amine is technical grade triethylene tetramine, and described solvent is tap water;
Second step, under stirring to add in above-mentioned solution with amine in the amido functional group ratio carboxylic acid that is 1:4, described carboxylic acid is industrial glucose acid;
The 3rd step, is heated to 60 DEG C by said mixture, all dissolves to it;
The 4th step, boils off solvent in said mixture, is cooled to room temperature;
The 5th step, is transferred to said mixture in mortar, and the Repone K that to add with amine and carboxylic acid total mass ratio be 0.5:1 grinds evenly, obtains swollen dose of the anti-swollen contracting of small molecules, and described Repone K is technical grade product.
When application, the anti-swollen dose of consumption of swollen contracting of small molecules is 0.5% of oilfield working fluids quality, and its anti-swollen rate to clay is 76%, and the swollen rate that contracts is 33%.
Embodiment 5
The preparation that the anti-swollen contracting of small molecules is swollen dose, comprises the following steps:
The first step is dissolved in amine in the solvent of 30 times in reactor, stir, described amine be amount of substance than technical grade trolamine and tetraethylene pentamine mixture for 1:1, described solvent is that volume ratio is the industrial grade benzenemethanol of 1:1 and the mixture of tap water;
Second step, under stirring to add in above-mentioned solution with amine in the amido functional group ratio carboxylic acid that is 1:1, described carboxylic acid is technical grade citric acid;
The 3rd step, is heated to 50 DEG C by said mixture, all dissolves to it;
The 4th step, boils off solvent in said mixture, is cooled to room temperature;
The 5th step, is transferred to said mixture in mortar, and the Repone K that to add with amine and carboxylic acid total mass ratio be 0.5:1 grinds evenly, obtains swollen dose of the anti-swollen contracting of small molecules, and described Repone K is technical grade product.
When application, the anti-swollen dose of consumption of swollen contracting of small molecules is 0.5% of oilfield working fluids quality, and its anti-swollen rate to clay is 61%, and the swollen rate that contracts is 32%.
Embodiment 6
The preparation that the anti-swollen contracting of small molecules is swollen dose, comprises the following steps:
The first step is dissolved in amine in the solvent of 10 times in reactor, stirs, and described amine is chemical pure quadrol, and described solvent is that volume ratio is the industrial grade benzenemethanol of 1:3 and the mixture of tap water;
Second step, under stirring to add in above-mentioned solution with amine in the amido functional group ratio carboxylic acid that is 1:2, described carboxylic acid is that amount of substance is than technical grade lactic acid and L-glutamic acid mixture for 1:1;
The 3rd step, is heated to 40 DEG C by said mixture, all dissolves to it;
The 4th step, boils off solvent in said mixture, is cooled to room temperature;
The 5th step, is transferred to said mixture in mortar, and the Repone K that to add with amine and carboxylic acid total mass ratio be 1.5:1 grinds evenly, obtains swollen dose of the anti-swollen contracting of small molecules, and described Repone K is technical grade product.
When application, the anti-swollen dose of consumption of swollen contracting of small molecules is 0.3% of oilfield working fluids quality, and its anti-swollen rate to clay is 80%, and the swollen rate that contracts is 21%.

Claims (8)

1.一种小分子防膨缩膨剂的制备，其特征在于，包括以下步骤： 1. the preparation of a small molecule anti-expansion shrinkage agent, is characterized in that, comprises the following steps: 第一步，在反应釜中将胺溶于5-30倍的溶剂中，搅拌均匀，所述的胺为工业级及其以上纯度的乙醇胺、二乙醇胺、三乙醇胺、乙二胺、二乙烯三胺、三乙烯四胺、四乙烯五胺、五乙烯六胺及其混合物，所述溶剂为工业级及其以上纯度甲醇、乙醇或者自来水以上纯度的水及其混合物；  In the first step, dissolve the amine in the solvent of 5-30 times in the reaction kettle and stir evenly. The amine is ethanolamine, diethanolamine, triethanolamine, ethylenediamine, diethylenetri Amines, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and mixtures thereof, the solvents are methanol, ethanol of industrial grade and above purity, or water of purity above tap water and mixtures thereof; 第二步，搅拌下向上述溶液中加入与胺中氨基官能团比例为1: 1-5的羧酸，所述羧酸为工业级及其以上纯度的乳酸、苹果酸、酒石酸、柠檬酸、葡萄糖酸、谷氨酸及其混合物；  In the second step, adding the carboxylic acid with the amino functional group ratio in the amine to the above solution under stirring is 1: 1-5, and the carboxylic acid is lactic acid, malic acid, tartaric acid, citric acid, glucose of industrial grade and above purity Acids, glutamic acid and mixtures thereof; 第三步，将上述混合物加热至30-100℃，至其全部溶解； The third step is to heat the above mixture to 30-100°C until it is completely dissolved; 第四步，将上述混合物中溶剂蒸去，冷却至室温； The fourth step is to evaporate the solvent in the above mixture and cool to room temperature; 第五步，将上述混合物转移至研钵中，加入与胺和羧酸总质量比为5-0.5: 1的氯化钾，研磨均匀，即得到小分子防膨缩膨剂，所述氯化钾为工业级及其以上纯度的产品。 The fifth step is to transfer the above mixture to a mortar, add potassium chloride with a total mass ratio of amine and carboxylic acid of 5-0.5: 1, and grind evenly to obtain a small molecule anti-expansion agent. Potassium is a product of industrial grade and above purity. 2.根据权利要求1所述的一种小分子防膨缩膨剂的制备，其特征在于：应用时，小分子防膨缩膨剂用量为油田工作液质量的0.1-2.0%，其对黏土的防膨率为50-80%，缩膨率大于20%。 2. the preparation of a kind of small molecule anti-swelling and shrinking agent according to claim 1 is characterized in that: during application, the amount of small molecule anti-swelling and shrinking agent is 0.1-2.0% of the oilfield working fluid quality, and its effect on clay The anti-expansion rate is 50-80%, and the shrinkage rate is greater than 20%. 3.根据权利要求1所述的一种小分子防膨缩膨剂的制备，其特征在于，包括以下步骤： 3. the preparation of a kind of small molecule anti-expansion shrinkage agent according to claim 1, is characterized in that, comprises the following steps: 第一步，在反应釜中将胺溶于5倍的溶剂中，搅拌均匀，所述的胺为工业级二乙醇胺，所述溶剂为工业级甲醇；  In the first step, the amine is dissolved in 5 times of the solvent in the reactor, and stirred evenly, the amine is industrial grade diethanolamine, and the solvent is industrial grade methanol; 第二步，搅拌下向上述溶液中加入与胺中氨基官能团比例为1: 1的羧酸，所述羧酸为工业级及其以上纯度的乳酸；  In the second step, under stirring, adding to the above-mentioned solution with the amino functional group ratio in the amine is a carboxylic acid of 1: 1, and the carboxylic acid is lactic acid of industrial grade and above purity; 第三步，将上述混合物加热至30℃，至其全部溶解； The third step is to heat the above mixture to 30°C until it is completely dissolved; 第四步，将上述混合物中溶剂蒸去，冷却至室温； The fourth step is to evaporate the solvent in the above mixture and cool to room temperature; 第五步，将上述混合物转移至研钵中，加入与胺和羧酸总质量比为5: 1的氯化钾，研磨均匀，即得到小分子防膨缩膨剂，所述氯化钾为工业级及其以上纯度的产品。 The 5th step, above-mentioned mixture is transferred in the mortar, add the potassium chloride that is 5: 1 with the total mass ratio of amine and carboxylic acid, grind evenly, promptly obtain small molecule anti-expansion shrinkage agent, described potassium chloride is Products of industrial grade and above purity. 4.根据权利要求1所述的一种小分子防膨缩膨剂的制备，其特征在于，包括以下步骤： 4. the preparation of a kind of small molecule anti-expansion shrinkage agent according to claim 1, is characterized in that, comprises the following steps: 第一步，在反应釜中将胺溶于8倍的溶剂中，搅拌均匀，所述的胺为工业级三乙醇胺，所述溶剂为化学纯乙醇；  In the first step, the amine is dissolved in 8 times of the solvent in the reaction kettle, and stirred evenly. The amine is technical grade triethanolamine, and the solvent is chemically pure ethanol; 第二步，搅拌下向上述溶液中加入与胺中氨基官能团比例为1:1的羧酸，所述羧酸为工业级酒石酸；  Second step, under stirring, add the carboxylic acid that is 1:1 with the amino functional group ratio in amine to above-mentioned solution, and described carboxylic acid is technical grade tartaric acid; 第三步，将上述混合物加热至40℃，至其全部溶解； In the third step, the above mixture is heated to 40°C until it is completely dissolved; 第四步，将上述混合物中溶剂蒸去，冷却至室温； The fourth step is to evaporate the solvent in the above mixture and cool to room temperature; 第五步，将上述混合物转移至研钵中，加入与胺和羧酸总质量比为3: 1的氯化钾，研磨均匀，即得到小分子防膨缩膨剂，所述氯化钾为工业级及其以上纯度的产品。 The 5th step, above-mentioned mixture is transferred in the mortar, add the potassium chloride that is 3: 1 with the total mass ratio of amine and carboxylic acid, grind evenly, promptly obtain small molecule anti-expansion shrinkage agent, described potassium chloride is Products of industrial grade and above purity. 5.根据权利要求1所述的一种小分子防膨缩膨剂的制备，其特征在于，包括以下步骤： 5. the preparation of a kind of small molecule anti-expansion shrinkage agent according to claim 1, is characterized in that, comprises the following steps: 第一步，在反应釜中将胺溶于15倍的溶剂中，搅拌均匀，所述的胺为分析纯二乙烯三胺，所述溶剂为分析纯甲醇；  In the first step, the amine is dissolved in 15 times of the solvent in the reactor, and stirred evenly, the amine is analytically pure diethylenetriamine, and the solvent is analytically pure methanol; 第二步，搅拌下向上述溶液中加入与胺中氨基官能团比例为1: 3的羧酸，所述羧酸为化学纯柠檬酸；  In the second step, under stirring, adding to the above-mentioned solution with the amino functional group ratio in the amine is a carboxylic acid of 1: 3, and the carboxylic acid is chemically pure citric acid; 第三步，将上述混合物加热至55℃，至其全部溶解； In the third step, the above mixture is heated to 55°C until it is completely dissolved; 第四步，将上述混合物中溶剂蒸去，冷却至室温； The fourth step is to evaporate the solvent in the above mixture and cool to room temperature; 第五步，将上述混合物转移至研钵中，加入与胺和羧酸总质量比为1: 1的氯化钾，研磨均匀，即得到小分子防膨缩膨剂，所述氯化钾为工业级产品。 The 5th step, above-mentioned mixture is transferred in the mortar, adds the potassium chloride that is 1: 1 with the total mass ratio of amine and carboxylic acid, grinds evenly, promptly obtains small molecule anti-swelling agent, described potassium chloride is Industrial grade product. 6.根据权利要求1所述的一种小分子防膨缩膨剂的制备，其特征在于，包括以下步骤： 6. the preparation of a kind of small molecule anti-expansion shrinkage agent according to claim 1, is characterized in that, comprises the following steps: 第一步，在反应釜中将胺溶于20倍的溶剂中，搅拌均匀，所述的胺为工业级三乙烯四胺，所述溶剂为自来水；  In the first step, the amine is dissolved in 20 times of the solvent in the reaction kettle and stirred evenly. The amine is technical grade triethylenetetramine, and the solvent is tap water; 第二步，搅拌下向上述溶液中加入与胺中氨基官能团比例为1: 4的羧酸，所述羧酸为工业级葡萄糖酸；  Second step, under stirring, add the carboxylic acid that is 1: 4 with the ratio of aminofunctional group in amine to above-mentioned solution, and described carboxylic acid is technical grade gluconic acid; 第三步，将上述混合物加热至60℃，至其全部溶解； In the third step, the above mixture is heated to 60°C until it is completely dissolved; 第四步，将上述混合物中溶剂蒸去，冷却至室温； In the fourth step, the solvent in the above mixture is evaporated and cooled to room temperature; 第五步，将上述混合物转移至研钵中，加入与胺和羧酸总质量比为0.5: 1的氯化钾，研磨均匀，即得到小分子防膨缩膨剂，所述氯化钾为工业级产品。 The 5th step, above-mentioned mixture is transferred in the mortar, adds the potassium chloride that is 0.5: 1 with the total mass ratio of amine and carboxylic acid, grinds evenly, promptly obtains small molecule anti-swelling agent, described potassium chloride is Industrial grade product. 7.根据权利要求1所述的一种小分子防膨缩膨剂的制备，其特征在于，包括以下步骤： 7. The preparation of a kind of small molecule anti-expansion shrinkage agent according to claim 1, is characterized in that, comprises the following steps: 第一步，在反应釜中将胺溶于30倍的溶剂中，搅拌均匀，所述的胺为物质的量比为1:1的工业级三乙醇胺和四乙烯五胺混合物，所述溶剂为体积比为1:1的工业级甲醇和自来水的混合物；  In the first step, the amine is dissolved in 30 times of the solvent in the reactor and stirred evenly. The amine is a mixture of technical grade triethanolamine and tetraethylenepentamine with a substance ratio of 1:1, and the solvent is A mixture of industrial grade methanol and tap water with a volume ratio of 1:1; 第二步，搅拌下向上述溶液中加入与胺中氨基官能团比例为1: 1的羧酸，所述羧酸为工业级柠檬酸；  Second step, under stirring, add the carboxylic acid that is 1: 1 with the ratio of aminofunctional group in amine to above-mentioned solution, described carboxylic acid is technical grade citric acid; 第三步，将上述混合物加热至50℃，至其全部溶解； In the third step, the above mixture is heated to 50°C until it is completely dissolved; 第四步，将上述混合物中溶剂蒸去，冷却至室温； The fourth step is to evaporate the solvent in the above mixture and cool to room temperature; 第五步，将上述混合物转移至研钵中，加入与胺和羧酸总质量比为0.5: 1的氯化钾，研磨均匀，即得到小分子防膨缩膨剂，所述氯化钾为工业级产品。 The 5th step, above-mentioned mixture is transferred in the mortar, adds the potassium chloride that is 0.5: 1 with the total mass ratio of amine and carboxylic acid, grinds evenly, promptly obtains small molecule anti-swelling agent, described potassium chloride is Industrial grade product. 8.根据权利要求1所述的一种小分子防膨缩膨剂的制备，其特征在于，包括以下步骤： 8. The preparation of a kind of small molecule anti-expansion shrinkage agent according to claim 1, is characterized in that, comprises the following steps: 第一步，在反应釜中将胺溶于10倍的溶剂中，搅拌均匀，所述的胺为化学纯乙二胺，所述溶剂为体积比为1:3的工业级甲醇和自来水的混合物；  In the first step, the amine is dissolved in 10 times the solvent in the reaction kettle and stirred evenly. The amine is chemically pure ethylenediamine, and the solvent is a mixture of industrial grade methanol and tap water with a volume ratio of 1:3 ; 第二步，搅拌下向上述溶液中加入与胺中氨基官能团比例为1: 2的羧酸，所述羧酸为物质的量比为1:1的工业级乳酸和谷氨酸混合物；  In the second step, under stirring, adding to the above-mentioned solution with the amino functional group ratio in the amine is a carboxylic acid of 1: 2, and the carboxylic acid is a mixture of technical grade lactic acid and glutamic acid with a substance ratio of 1: 1; 第三步，将上述混合物加热至40℃，至其全部溶解； In the third step, the above mixture is heated to 40°C until it is completely dissolved; 第四步，将上述混合物中溶剂蒸去，冷却至室温； The fourth step is to evaporate the solvent in the above mixture and cool to room temperature; 第五步，将上述混合物转移至研钵中，加入与胺和羧酸总质量比为1.5: 1的氯化钾，研磨均匀，即得到小分子防膨缩膨剂，所述氯化钾为工业级产品。 The 5th step, above-mentioned mixture is transferred in the mortar, adds the potassium chloride that is 1.5: 1 with the total mass ratio of amine and carboxylic acid, grinds evenly, promptly obtains small molecule anti-expansion shrinkage agent, described potassium chloride is Industrial grade product.
CN201410067571.7A 2014-02-27 2014-02-27 Preparation method and application of micro-molecular anti-swelling shrinkage agent Pending CN103865507A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410067571.7A CN103865507A (en) 2014-02-27 2014-02-27 Preparation method and application of micro-molecular anti-swelling shrinkage agent

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410067571.7A CN103865507A (en) 2014-02-27 2014-02-27 Preparation method and application of micro-molecular anti-swelling shrinkage agent

Publications (1)

Publication Number Publication Date
CN103865507A true CN103865507A (en) 2014-06-18

Family

ID=50904533

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410067571.7A Pending CN103865507A (en) 2014-02-27 2014-02-27 Preparation method and application of micro-molecular anti-swelling shrinkage agent

Country Status (1)

Country Link
CN (1) CN103865507A (en)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105219361A (en) * 2015-10-20 2016-01-06 中国石油集团渤海钻探工程有限公司 Water-soluble high-density weighting material and preparation method thereof
CN105219360A (en) * 2015-10-20 2016-01-06 中国石油集团渤海钻探工程有限公司 Bore completion water-soluble high-density weighting material and preparation method thereof
CN105219357A (en) * 2015-10-20 2016-01-06 中国石油集团渤海钻探工程有限公司 Oilfield drilling completion water-soluble high-density weighting material and preparation method thereof
CN105670574A (en) * 2014-11-21 2016-06-15 中石化胜利石油工程有限公司钻井工艺研究院 Drilling fluid ether-amine compound inhibitor and preparation method thereof
CN107434971A (en) * 2016-05-27 2017-12-05 中国石油天然气股份有限公司 Anti-swelling and shrinkage-swelling agent for water injection well and preparation method and application thereof
CN108715755A (en) * 2018-06-27 2018-10-30 长江大学 A kind of Swelling-resistant shrinking and swelling agent and preparation method thereof
CN109694697A (en) * 2017-10-23 2019-04-30 中石化石油工程技术服务有限公司 A kind of drilling fluid polyamine shale inhibitor and preparation method thereof and drilling fluid
CN112443301A (en) * 2020-12-02 2021-03-05 西安石油大油气科技有限公司 Method for improving crude oil recovery ratio by integrating oil displacement and pressure reduction
CN114479804A (en) * 2020-11-11 2022-05-13 中国石油天然气股份有限公司 Blocking remover and preparation method and application thereof
CN115838590A (en) * 2021-09-18 2023-03-24 中国石油化工股份有限公司 A low-cost and high-efficiency anti-swelling agent for fracturing, its preparation method and use method
CN116376528A (en) * 2023-03-30 2023-07-04 天津新翔油气技术有限公司 Anti-swelling shrinkage sand-inhibiting agent, preparation method and application thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009079535A1 (en) * 2007-12-18 2009-06-25 E.I. Du Pont De Nemours And Company Process to prepare zirconium-based cross-linker compositions and their use in oil field applications
CN101492599B (en) * 2009-02-28 2011-01-05 成都孚吉科技有限公司 Foaming water discharge agent and its preparation
CN102443124B (en) * 2011-09-21 2013-04-10 西安石油大学 Preparation method and application of multifunctional polyamine amide for oil field
CN102250601B (en) * 2011-05-06 2013-04-17 河北科技大学 Composite blocking remover for oil well and application method thereof
CN102250603B (en) * 2011-05-06 2013-06-26 河北科技大学 A segmented injection type oil well composite plugging remover and its injection method
CN102703045B (en) * 2012-06-18 2013-11-06 长江大学 Multi-slug composite pressure decreasing and injection increasing agent for ultra-low permeability oil field

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009079535A1 (en) * 2007-12-18 2009-06-25 E.I. Du Pont De Nemours And Company Process to prepare zirconium-based cross-linker compositions and their use in oil field applications
CN101492599B (en) * 2009-02-28 2011-01-05 成都孚吉科技有限公司 Foaming water discharge agent and its preparation
CN102250601B (en) * 2011-05-06 2013-04-17 河北科技大学 Composite blocking remover for oil well and application method thereof
CN102250603B (en) * 2011-05-06 2013-06-26 河北科技大学 A segmented injection type oil well composite plugging remover and its injection method
CN102443124B (en) * 2011-09-21 2013-04-10 西安石油大学 Preparation method and application of multifunctional polyamine amide for oil field
CN102703045B (en) * 2012-06-18 2013-11-06 长江大学 Multi-slug composite pressure decreasing and injection increasing agent for ultra-low permeability oil field

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105670574A (en) * 2014-11-21 2016-06-15 中石化胜利石油工程有限公司钻井工艺研究院 Drilling fluid ether-amine compound inhibitor and preparation method thereof
CN105219361A (en) * 2015-10-20 2016-01-06 中国石油集团渤海钻探工程有限公司 Water-soluble high-density weighting material and preparation method thereof
CN105219360A (en) * 2015-10-20 2016-01-06 中国石油集团渤海钻探工程有限公司 Bore completion water-soluble high-density weighting material and preparation method thereof
CN105219357A (en) * 2015-10-20 2016-01-06 中国石油集团渤海钻探工程有限公司 Oilfield drilling completion water-soluble high-density weighting material and preparation method thereof
CN107434971A (en) * 2016-05-27 2017-12-05 中国石油天然气股份有限公司 Anti-swelling and shrinkage-swelling agent for water injection well and preparation method and application thereof
CN109694697A (en) * 2017-10-23 2019-04-30 中石化石油工程技术服务有限公司 A kind of drilling fluid polyamine shale inhibitor and preparation method thereof and drilling fluid
CN108715755A (en) * 2018-06-27 2018-10-30 长江大学 A kind of Swelling-resistant shrinking and swelling agent and preparation method thereof
CN114479804A (en) * 2020-11-11 2022-05-13 中国石油天然气股份有限公司 Blocking remover and preparation method and application thereof
CN112443301A (en) * 2020-12-02 2021-03-05 西安石油大油气科技有限公司 Method for improving crude oil recovery ratio by integrating oil displacement and pressure reduction
CN115838590A (en) * 2021-09-18 2023-03-24 中国石油化工股份有限公司 A low-cost and high-efficiency anti-swelling agent for fracturing, its preparation method and use method
CN116376528A (en) * 2023-03-30 2023-07-04 天津新翔油气技术有限公司 Anti-swelling shrinkage sand-inhibiting agent, preparation method and application thereof

Similar Documents

Publication Publication Date Title
CN103865507A (en) Preparation method and application of micro-molecular anti-swelling shrinkage agent
CN103881694B (en) A low dosage guar polynuclear crosslinking agent
CN109486476B (en) Viscoelastic surfactant for high-temperature self-diverting acid, preparation method and application
CN101812290A (en) Acid clean fracturing fluid and preparation method thereof
CN103497753B (en) One is applicable to the of the fracturing fluid linking agent of concentrated water
WO2014082420A1 (en) Working substance pair for absorptive heat circulation system with heat source temperature between 60°c and 130°c
CN104073235A (en) Long-carbon-chain amide glycine betaine clean fracturing fluid and preparation method thereof
CN102071427B (en) Corrosion inhibitor for inhibiting corrosion of high-temperature high-pressure carbon dioxide and preparation method thereof
CN102352232A (en) Temperature-resistant and salt-resistant polymer clean fracturing fluid thickening agent and preparation method thereof
CN105860943A (en) Inhibited type starch filtrate reducer for drilling fluid and preparation method of inhibited type starch filtrate reducer
CN102660246A (en) Precoated sand used for sand prevention for intermediate and low temperate oil deposit and preparation method thereof
CN105838342A (en) High-density cationic saccharide inhibitor for drilling fluids and preparation method thereof
CN103756663A (en) High performance acidizing fracturing fluid and preparation method thereof
CN105131926B (en) A kind of preparation method of foaming water discharge corrosion inhibiter
CN106905948A (en) A kind of micro- residue, the guar gum clean fracturing fluid of weak injury
CN103865502A (en) Preparation method and application of micromolecule clay expansion inhibitor
CN104559991B (en) A kind of surfactant and its preparation method and application
CN110790676A (en) A new type of salt-resistant and temperature-resistant zwitterionic viscoelastic surfactant and preparation method of reservoir stimulation working fluid
CN102585797B (en) Diverting acid for carrying out acidification and transformation on high-temperature oil and gas well with long well segment
CN115850659A (en) Self-degradation leak-proof plugging agent for protecting reservoir for drilling fluid and preparation method and application thereof
CN103113874A (en) Organic titanium crosslinking agent, and preparation method and application method thereof
CN102154001B (en) Method for preparing solid organic boron delayed cross-linking agent
CN111205840B (en) Blocking remover based on deep eutectic solvent and preparation method thereof
CN114990556A (en) A high-efficiency corrosion inhibitor used in lactic acid corrosion conditions
CN103571442B (en) A kind of preparation method and application of the clay inhibitor of melamine-derived

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20140618

RJ01 Rejection of invention patent application after publication