CN109021950B - Solid chelating acid for increasing injection of water injection well and preparation method thereof - Google Patents
Solid chelating acid for increasing injection of water injection well and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a solid chelating acid for increasing injection of a water injection well and a preparation method thereof, relating to the technical field of depressurization and increase injection of the water injection well of an oil field, wherein the solid chelating acid for increasing injection of the water injection well comprises the following raw materials in percentage by weight: 30-40% of main agent, 20-30% of auxiliary agent, 10-15% of reinforcing agent, 3-8% of active agent, 2-3% of inhibitor, 5-10% of stabilizer and 15-30% of adhesive. The invention can reduce the potential safety hazard in the processes of transportation, storage and use in the acidification and blockage removal, greatly improve the acid liquor slow release rate, enlarge the blockage removal radius, facilitate the deep blockage removal of the water injection well and improve the effective rate of the pressure reduction and injection increase measures of the water injection well.
Description
Technical Field
The invention relates to a solid chelating acid, in particular to a solid chelating acid for increasing injection of a water injection well and a preparation method thereof. Belongs to the technical field of pressure reduction and injection increase of oil field water injection wells.
Background
As the development time of an oil field increases, the production of the oil well decreases due to the decrease of the formation energy, and water injection development is required to maintain the formation energy. In water injection development, water injection wells exhibit high pressure underinjection due to plugging by factors such as injected water mechanical impurities, scaling and bacterial corrosion products. The water injection well needs to be subjected to deblocking operation, the existing common deblocking agent is composed of acid liquor, the acid liquor belongs to dangerous chemicals, and the acid liquor has potential environmental protection hazards and potential metal corrosion safety hazards caused by the acid liquor in the processes of transportation, storage and use; meanwhile, the acid solution and the mineral in the reservoir have high reaction speed, and the problems of excessive corrosion of a near shaft and deep blockage removal limitation caused by small blockage removal radius exist. With the implementation of a new environment-friendly method and the supervision requirement of a safety production method, the acidification blockage removal needs to follow up the technical development requirement, and a blockage removal product beneficial to the transportation, storage and use of acid liquor is developed.
In addition, chinese patent No. CN102775980A, 11/2012 discloses an acidification blocking remover suitable for complex lithologic reservoir. The components and the mixture ratio are as follows by weight percent: 0-12% of hydrochloric acid, 0-3% of ammonium bifluoride, 0-10% of sulfamic acid, 0-5% of fluoboric acid, 0-3% of boric acid, 0-4% of ethanol, 0-2% of triethanolamine, 3% of glacial acetic acid, 4.0-6.0% of corrosion inhibitor, 2.0-4.0% of mutual solvent, 0.5-1.0% of penetrating agent, 2.0% of clay stabilizer and 45-88.5% of water. The problems that the lithology and physical property difference of an oil field is large, and the acidizing and blockage removing construction effect of a conventional water injection well is not ideal when the conventional water injection well is used in staggered distribution are mainly solved. The acidizing blocking remover suitable for the complex lithologic reservoir can effectively erode formation minerals and plugs, does not damage rock stratum frameworks, can prevent secondary precipitation caused by sensitive minerals from being generated, improves the water absorption capacity of an oil layer, and increases the daily increase of water injection amount of an average single well measure. Chinese patent No. CN104194759A, 12 months and 10 days 2014 discloses a neutral blocking remover composition for an oil extraction stratum of an oil field, which is prepared from the following raw materials in parts by weight: 30-36 parts of sodium polyepoxysuccinate, 18-25 parts of sodium gluconate, 2-3 parts of polyethylene glycol, 2-4 parts of triethanolamine, 9-12 parts of ethyl lactate, 7-10 parts of fatty alcohol-polyoxyethylene ether sodium sulfate, 8-12 parts of sodium amino acid, 10-15 parts of active attapulgite, 0.1-0.2 part of vanadium pentoxide, 5-7 parts of lipase, 5-8 parts of sorbitan fatty acid ester, 15-18 parts of sodium p-hydroxysulfonate, 3-7 parts of tert-butyl hydroperoxide and 0.1-0.3 part of diethylene glycol laurate. The plugging removal agent has the advantages of high plugging removal speed, neutrality, no corrosion, capability of quickly dissolving material scale, asphalt sediment scale, carbonate scale, silicate scale and the like generated by a ternary composite flooding system, self-degradation of plugging removal waste liquid, no need of returning to the ground for sewage treatment, cleaning of oil field stratum plugging removal, no corrosion, no dead angle, no generation of sediment and secondary well plugging, and no more than 24 hours of plugging removal treatment time.
The blockage removing product represented by the patent is mainly characterized in that liquid acid liquor is compounded for blockage removal, or solid complexing agent is subjected to blockage removal through complexation. The potential safety hazard of the acid liquor in the processes of transportation, storage and use is large, and the blockage removal radius is small due to quick reaction; although the solid complexing agent avoids the defects of transportation and storage of liquid acid liquid, the problem of insufficient blockage removing capability exists, and meanwhile, the pertinence to water injection well blockages is poor. In order to meet the requirements of a new environmental protection method, the plugging removal technology of the oil field water injection well needs to develop a solid chelated acid product which can better solve the problems, in particular to the requirements of pressure reduction and injection increase of the water injection well of the low permeability oil reservoir.
Disclosure of Invention
The invention aims to provide a solid chelating acid for increasing injection of a water injection well and a preparation method thereof, which overcome the problems of safety and environmental protection of conventional acid liquid in the processes of transportation, storage and use, and simultaneously solve the problems of high acid liquid reaction rate, small blockage removal radius, excessive corrosion of a near-wellbore, serious sand production of the near-wellbore after measures, short effective period of the measure well, frequent measures of the water injection well and increased development cost of the oil field in the conventional acidification. The solid chelating acid provided by the invention is in a solid state, does not contact water, is not corroded, does not need to be transported by a special vehicle for dangerous chemical tanks, and is convenient to store and use; after the solid chelating acid provided by the invention is used for preparing the solution, the solid chelating acid needs to be ionized to generate acid liquor, so that the slow release rate of the acid liquor is reduced, the slow release performance is improved, the blockage removing radius is enlarged, the blockage removal of the deep blockage of the water injection well can be realized, the effective rate of measures is improved, and the effective period of measures is prolonged.
In order to achieve the purpose, the invention adopts the technical scheme that: a solid chelating acid for increasing injection of a water injection well is characterized in that: the material comprises the following raw materials in percentage by weight: 30-40% of main agent, 20-30% of auxiliary agent, 10-15% of reinforcing agent, 3-8% of active agent, 2-3% of inhibitor, 5-10% of stabilizer and 15-30% of adhesive.
The main agent consists of one or two of hydrazine hydrochloride and hydrazine dihydrochloride, sulfamic acid and hydroxyethylidene diphosphonic acid, and the weight percentage of the main agent is 30-40 percent: 10-15% of one or two of hydrazine hydrochloride and hydrazine dihydrochloride, 10-12% of sulfamic acid and 10-13% of hydroxyethylidene diphosphonic acid, wherein the mass percentage of the hydroxyethylidene diphosphonic acid is 90%.
The auxiliary agent consists of 20-30 wt% of urea nitrate and 5-10 wt% of urea phosphate.
The reinforcing agent consists of ammonium bifluoride and ammonium fluoroborate, wherein the weight percentage of the reinforcing agent is 10-15%, the weight percentage of the ammonium bifluoride is 5-7%, and the weight percentage of the ammonium fluoroborate is 5-8%.
The active agent is 2,3,7, 9-tetramethyl-5-decyne-4, 7-diol polyoxyethylene ether.
The inhibitor is tropaeolum hydroxyethyl imidazoline.
The stabilizer consists of 5-10 wt% of isoascorbic acid and 2-4 wt% of nitrilotriacetic acid.
The adhesive consists of 15-30 wt% of stearic acid 1801 and Span-60, wherein the stearic acid 1801 accounts for 10-20 wt% and the Span-60 accounts for 5-10 wt%.
A preparation method of solid chelating acid for increasing injection of a water injection well is characterized by comprising the following steps:
step 1), preparing materials, weighing the raw materials of the solid chelating acid for increasing injection of the water injection well according to the formula:
30-40% of main agent, 20-30% of auxiliary agent, 10-15% of reinforcing agent, 3-8% of active agent, 2-3% of inhibitor, 5-10% of stabilizer and 15-30% of adhesive;
step 2) grinding the adhesive with the formula amount by a grinder under the protection of liquid nitrogen until the adhesive passes through 100 meshes to obtain powder for later use;
step 3) raising the temperature in the kneader, controlling the constant temperature at 40-42 ℃, adding the main agent with the formula amount, and stirring for 20-30 min; adding inhibitor, enhancer and adjuvant, and stirring for 30-50 min;
step 4) cooling the mixture obtained in the step 3), sieving the mixture by using a 30-50-mesh sieve, and continuously kneading the mixture which does not pass through the sieve in a kneader until the mixture completely passes through the 30-50-mesh sieve; adding the mixture passing through the screen into the kneader again, controlling the constant temperature at 50-52 ℃, adding the active agent and the stabilizing agent according to the formula amount, and stirring for 20-30 min;
step 5) slowly adding the ground powder in the step 2) into the mixture mixed in the step 4), and stirring for 20-30 min; and (3) closing the temperature of the kneader, continuing stirring for 20-30min, sieving by using a 20-40 mesh sieve, and continuing kneading without passing through the sieve until all the solid chelate acid passes through the 20-40 mesh sieve, namely the solid chelate acid for increasing injection of a water injection well.
The main agent consists of one or two of hydrazine hydrochloride and hydrazine dihydrochloride, sulfamic acid and hydroxyethylidene diphosphonic acid, and the weight percentage of the main agent is 30-40 percent: 10-15% of one or two of hydrazine hydrochloride and hydrazine dihydrochloride, 10-12% of sulfamic acid and 10-13% of hydroxyethylidene diphosphonic acid; the auxiliary agent consists of urea nitrate and urea phosphate, wherein the weight percentage of the auxiliary agent is 20-30%, the weight percentage of the urea nitrate is 15-20%, and the weight percentage of the urea phosphate is 5-10%; the reinforcing agent consists of ammonium bifluoride and ammonium fluoroborate, wherein in the reinforcing agent with the weight percentage of 10-15%, the weight percentage of the ammonium bifluoride is 5-7%, and the weight percentage of the ammonium fluoroborate is 5-8%; the active agent is 2,3,7, 9-tetramethyl-5-decyne-4, 7-diol polyoxyethylene ether; the inhibitor is tropyl hydroxyethyl imidazoline; the stabilizer consists of 5-10 wt% of isoascorbic acid and 2-4 wt% of nitrilotriacetic acid, wherein the isoascorbic acid accounts for 3-6 wt% of the stabilizer; the adhesive consists of 15-30 wt% of stearic acid 1801 and Span-60, wherein the stearic acid 1801 accounts for 10-20 wt% and the Span-60 accounts for 5-10 wt%.
Compared with the prior art, the invention has the following advantages:
1. compared with the conventional acidized plugging removal liquid oil, the solid chelating acid is remarkably improved in the aspects of safety and environmental protection in the processes of transportation, storage and use of the material.
In the aspect of transportation: the solid chelating acid is solid particles, has small self corrosion, and can be transported by a truck by using a kraft paper packaging bag; the conventional acidizing plugging removal liquid needs to be transported by a special dangerous goods tank truck.
In terms of storage: the solid chelating acid is managed and stored according to chemicals, and the conventional acidification blockage removing liquid is managed and stored according to dangerous chemicals.
In the use aspect: the solid chelating acid is directly added into an acid liquid tank or a sand mixing tank, and active ingredients are slowly released in the flowing process, so that no acidic gas is released, and the corrosion to injection equipment and a water injection pipe string is extremely low; a large amount of acid gas is released in the use of the conventional acidizing plugging removal liquid, the acidity is strong, and the corrosion to metal equipment is serious.
Compared with the conventional acid solution, the solid chelating acid greatly reduces the cost in the processes of transportation, storage and use.
2. The solid chelating acid improves the slow release rate and the slow speed of the blockage removing working solution, enlarges the blockage removing radius, overcomes the phenomenon of excessive corrosion near a well barrel, and is beneficial to removing blockage caused by deep blockage of a water injection well.
In the invention, hydrazine hydrochloride, hydrazine dihydrochloride, sulfamic acid and hydroxyethylidene diphosphonic acid are all solid acids, and are slowly dissolved and released in water, so that the reaction rate of H + ions in rocks is greatly reduced; urea nitrate and urea phosphate are chemically decomposed to provide effective NO3 < - >, PO43 < - >, and the acid liquor blockage removal performance is promoted to be improved through the ion synergistic effect; the ammonium bifluoride and the ammonium fluoroborate improve the solubility of the working solution to silicate minerals such as feldspar in sandstone by ionizing F-ions. The ionic equilibrium in the chemical reaction of reactants is involved, and the effective ion concentration is slowly released, so that the slow release rate and the slow speed of the solid chelating acid working solution are further delayed. Under the condition of certain construction displacement, the working fluid can play a longer action distance in the reservoir. Meanwhile, the initial plugging removal capability of the working fluid is also relative to that of the conventional acidizing fluid, so that excessive corrosion of a near well bore is avoided. The 2,3,7, 9-tetramethyl-5-decyne-4, 7-diol polyoxyethylene ether has excellent interfacial tension reducing performance and permeability, reduces the emulsion blockage of the working solution, and improves the sweep performance of the working solution. The tropane oil-based hydroxyethyl imidazoline inhibits the corrosion of the working solution to metal, and avoids the introduction of extra Fe3+ in the working solution; the tropane oil-based hydroxyethyl imidazoline, the isoascorbic acid and the nitrilotriacetic acid can chelate free Fe3+ in the solution, so that the formation of acid sludge is reduced, and the damage of working solution to a reservoir is reduced. The stearic acid and Span-60 have the tasks of wrapping and bonding the solid chelating acid, improving the solid form of the chelating acid, being capable of synergistically slowing down the speed of the working solution, being in a liquid state at a certain temperature (60 ℃ and above), and not additionally increasing the damage of a reservoir stratum.
Drawings
The invention will be described in further detail with reference to the drawings and the detailed description, in which:
FIG. 1 is a schematic representation of the retarded comparison of solid chelated acid and earth acid (60 deg.C) for water injection well stimulation according to the present invention.
Detailed Description
Example 1
The invention discloses a solid chelating acid for increasing injection of a water injection well, which consists of the following raw materials in percentage by weight: 30-40% of main agent, 20-30% of auxiliary agent, 10-15% of reinforcing agent, 3-8% of active agent, 2-3% of inhibitor, 5-10% of stabilizer and 15-30% of adhesive.
Heating and kneading in the field are adopted to prepare the solid chelating acid for injection enhancement of the water injection well.
The preparation method of the solid chelating acid for increasing injection of the water injection well comprises the following specific steps:
step 1), preparing materials, weighing the raw materials of the solid chelating acid for increasing injection of the water injection well according to the formula:
30-40% of main agent, 20-30% of auxiliary agent, 10-15% of reinforcing agent, 3-8% of active agent, 2-3% of inhibitor, 5-10% of stabilizer and 15-30% of adhesive;
step 2) grinding the adhesive with the formula amount by a grinder under the protection of liquid nitrogen until the adhesive passes through 100 meshes to obtain powder for later use;
step 3) raising the temperature in the kneader, controlling the constant temperature at 40-42 ℃, adding the main agent with the formula amount, and stirring for 20-30 min; adding inhibitor, enhancer and adjuvant, and stirring for 30-50 min;
step 4) cooling the mixture obtained in the step 3), sieving the mixture by using a 30-50-mesh sieve, and continuously kneading the mixture which does not pass through the sieve in a kneader until the mixture completely passes through the 30-50-mesh sieve; adding the mixture passing through the screen into the kneader again, controlling the constant temperature at 50-52 ℃, adding the active agent and the stabilizing agent according to the formula amount, and stirring for 20-30 min;
step 5) slowly adding the ground powder in the step 2) into the mixture mixed in the step 4), and stirring for 20-30 min; and (3) closing the temperature of the kneader, continuing stirring for 20-30min, sieving by using a 20-40 mesh sieve, and continuing kneading without passing through the sieve until all the solid chelate acid passes through the 20-40 mesh sieve, namely the solid chelate acid for increasing injection of a water injection well.
The solid chelating acid for increasing the injection of the water injection well reduces the potential safety hazard in transportation, storage and use processes in acidification and blockage removal, greatly improves the acid liquor slow release rate, enlarges the blockage removal radius, and is beneficial to deep blockage removal of the water injection well.
Example 2
On the basis of the embodiment 1, the main agent consists of one or two of hydrazine hydrochloride and hydrazine dihydrochloride, sulfamic acid and hydroxyethylidene diphosphonic acid, and the weight percentage of the main agent is 30-40 percent: 10-15% of one or two of hydrazine hydrochloride and hydrazine dihydrochloride, 10-12% of sulfamic acid and 10-13% of hydroxyethylidene diphosphonic acid, wherein the mass percentage of the hydroxyethylidene diphosphonic acid is 90%. The auxiliary agent consists of 20-30 wt% of urea nitrate and 5-10 wt% of urea phosphate. The reinforcing agent consists of ammonium bifluoride and ammonium fluoroborate, wherein the weight percentage of the reinforcing agent is 10-15%, the weight percentage of the ammonium bifluoride is 5-7%, and the weight percentage of the ammonium fluoroborate is 5-8%. The active agent is 2,3,7, 9-tetramethyl-5-decyne-4, 7-diol polyoxyethylene ether. The inhibitor is tropaeolum hydroxyethyl imidazoline. The stabilizer consists of 5-10 wt% of isoascorbic acid and 2-4 wt% of nitrilotriacetic acid. The adhesive consists of 15-30 wt% of stearic acid 1801 and Span-60, wherein the stearic acid 1801 accounts for 10-20 wt% and the Span-60 accounts for 5-10 wt%.
Example 3
The preparation method of the solid chelating acid for increasing injection of the water injection well comprises the following specific steps:
step 1), preparing materials, weighing the raw materials of the solid chelating acid for increasing injection of the water injection well according to the formula:
30-40% of main agent, 20-30% of auxiliary agent, 10-15% of reinforcing agent, 3-8% of active agent, 2-3% of inhibitor, 5-10% of stabilizer and 15-30% of adhesive; the main agent consists of one or two of hydrazine hydrochloride and hydrazine dihydrochloride, sulfamic acid and hydroxyethylidene diphosphonic acid, and the weight percentage of the main agent is 30-40 percent: 10-15% of one or two of hydrazine hydrochloride and hydrazine dihydrochloride, 10-12% of sulfamic acid and 10-13% of hydroxyethylidene diphosphonic acid; the auxiliary agent consists of urea nitrate and urea phosphate, wherein the weight percentage of the auxiliary agent is 20-30%, the weight percentage of the urea nitrate is 15-20%, and the weight percentage of the urea phosphate is 5-10%; the reinforcing agent consists of ammonium bifluoride and ammonium fluoroborate, wherein in the reinforcing agent with the weight percentage of 10-15%, the weight percentage of the ammonium bifluoride is 5-7%, and the weight percentage of the ammonium fluoroborate is 5-8%; the active agent is 2,3,7, 9-tetramethyl-5-decyne-4, 7-diol polyoxyethylene ether; the inhibitor is tropyl hydroxyethyl imidazoline; the stabilizer consists of 5-10 wt% of isoascorbic acid and 2-4 wt% of nitrilotriacetic acid, wherein the isoascorbic acid accounts for 3-6 wt% of the stabilizer; the adhesive consists of 15-30 wt% of stearic acid 1801 and Span-60, wherein the stearic acid 1801 accounts for 10-20 wt% and the Span-60 accounts for 5-10 wt%.
Step 2) grinding stearic acid 1801 and Span-60 with formula amount by a grinder under the protection of liquid nitrogen until the stearic acid and Span-60 pass through 100 meshes to obtain powder for later use;
and 3) raising the temperature in the kneader, controlling the temperature to be 40-42 ℃, and adding hydrazine hydrochloride (or hydrazine dihydrochloride, or hydrazine hydrochloride and hydrazine dihydrochloride according to the weight ratio of 1: 1), sulfamic acid and hydroxyethylidene diphosphonic acid, and stirring for 20-30 min; then adding the tropane oil-based hydroxyethyl imidazoline according to the formula amount, immediately adding the ammonium bifluoride and the ammonium fluoroborate according to the formula amount and the urea nitrate and the urea phosphate according to the formula amount, and stirring for 30-50 min;
step 4) cooling the mixture obtained in the step 3), sieving the mixture by using a 30-50-mesh sieve, and continuously kneading the mixture which does not pass through the sieve in a kneader until the mixture completely passes through the 30-50-mesh sieve; adding the mixture passing through the screen into the kneader again, controlling the constant temperature at 50-52 ℃, adding the 2,3,7, 9-tetramethyl-5-decyne-4, 7-diol polyoxyethylene ether and the isoascorbic acid and nitrilotriacetic acid according to the formula, and stirring for 20-30 min;
step 5) slowly adding the powder of all the stearic acid 1801 and Span-60 ground in the step 2) into the mixture mixed in the step 4), and stirring for 20-30 min; and (3) closing the temperature of the kneader, continuing stirring for 20-30min, sieving by using a 20-40 mesh sieve, and continuing kneading without passing through the sieve until all the solid chelate acid passes through the 20-40 mesh sieve, namely the solid chelate acid for increasing injection of a water injection well.
Example 4
Grinding 18% stearic acid 1801 and 10% Span-60 by a grinder under the protection of liquid nitrogen until the stearic acid passes through a 100-mesh sieve according to the weight percentage of the solid chelating acid occupied in the injection increase of the water injection well for standby. Firstly, raising the temperature in a kneader, controlling the temperature to be constant at 42 ℃, adding 5% of hydrazine hydrochloride, 5% of hydrazine dihydrochloride, 10% of sulfamic acid and 12% of hydroxyethylidene diphosphonic acid, wherein the mass percentage content of the hydroxyethylidene diphosphonic acid is 90%, and stirring for 30 min; then adding 2% of tropyl hydroxyethyl imidazoline, immediately adding 5% of ammonium bifluoride, 5% of ammonium fluoroborate, 15% of urea nitrate and 5% of urea phosphate, and stirring for 50 min; cooling the mixture, sieving the mixture by using a 50-mesh sieve, and continuously kneading the mixture which does not pass through the sieve until the mixture completely passes through the 50-mesh sieve; adding the mixture into a kneader, controlling the constant temperature at 52 ℃, adding 3% of 2,3,7, 9-tetramethyl-5-decyne-4, 7-diol polyoxyethylene ether, 3% of isoascorbic acid and 2% of nitrilotriacetic acid, and stirring for 30 min; slowly adding all the grinded stearic acid 1801 and Span-60 powder, and stirring for 30 min; and (3) closing the temperature of the kneader, continuing stirring for 30min, sieving by using a 40-mesh sieve, and continuing kneading until all the mixture which does not pass through the sieve passes through the 40-mesh sieve to obtain the solid chelating acid product for increasing the injection of the water injection well.
Example 5
Grinding 10% stearic acid 1801 and 5% Span-60 by a grinder under the protection of liquid nitrogen until the stearic acid passes through a 100-mesh sieve according to the weight percentage of the solid chelating acid occupied in the augmented injection of the water injection well for standby. Firstly, raising the temperature in a kneader, controlling the constant temperature at 40 ℃, adding 10% hydrazine dihydrochloride, 10% sulfamic acid and 10% hydroxyethylidene diphosphonic acid, wherein the mass percentage content of the hydroxyethylidene diphosphonic acid is 90%, and stirring for 20 min; then adding 2% of tropyl hydroxyethyl imidazoline, immediately adding 7% of ammonium bifluoride, 8% of ammonium fluoroborate, 15% of urea nitrate and 10% of urea phosphate, and stirring for 30 min; cooling the mixture, sieving the mixture by using a 30-mesh sieve, and continuously kneading the mixture which does not pass through the sieve until the mixture completely passes through the 30-mesh sieve; adding the mixture into a kneader, controlling the constant temperature at 50 ℃, adding 6% of 2,3,7, 9-tetramethyl-5-decyne-4, 7-diol polyoxyethylene ether, 3% of isoascorbic acid and 4% of nitrilotriacetic acid, and stirring for 20 min; slowly adding all the grinded stearic acid 1801 and Span-60 powder, and stirring for 20 min; and (3) closing the temperature of the kneader, continuing stirring for 20min, sieving by using a 20-mesh sieve, and continuing kneading until all the mixture which does not pass through the sieve passes through the 20-mesh sieve to obtain the solid chelating acid product for increasing the injection of the water injection well.
Example 6
Grinding 13% stearic acid 1801 and 7% Span-60 by a grinder under the protection of liquid nitrogen until the stearic acid passes through a 100-mesh sieve according to the weight percentage of the solid chelating acid occupied in the augmented injection of the water injection well for standby. Firstly, raising the temperature in a kneader, controlling the constant temperature at 41 ℃, adding 11 percent of hydrazine dihydrochloride, 11 percent of sulfamic acid and 11 percent of hydroxyethylidene diphosphonic acid, wherein the mass percent of the hydroxyethylidene diphosphonic acid is 90 percent, and stirring for 25 min; then adding 3% of tropyl hydroxyethyl imidazoline, immediately adding 6% of ammonium bifluoride, 6% of ammonium fluoroborate, 16% of urea nitrate and 6% of urea phosphate, and stirring for 40 min; cooling the mixture, sieving the mixture by using a 40-mesh sieve, and continuously kneading the mixture which does not pass through the sieve until the mixture completely passes through the 40-mesh sieve; adding the mixture into a kneader, controlling the constant temperature at 51 ℃, adding 4% of 2,3,7, 9-tetramethyl-5-decyne-4, 7-diol polyoxyethylene ether, 3% of isoascorbic acid and 3% of nitrilotriacetic acid, and stirring for 25 min; slowly adding all the grinded stearic acid 1801 and Span-60 powder, and stirring for 25 min; and (3) closing the temperature of the kneader, continuing stirring for 25min, sieving by using a 30-mesh sieve, and continuing kneading until all the mixture which does not pass through the sieve passes through the 30-mesh sieve to obtain the solid chelating acid product for increasing the injection of the water injection well.
In the invention, hydrazine hydrochloride, hydrazine dihydrochloride, sulfamic acid and hydroxyethylidene diphosphonic acid are all solid acids, and are slowly dissolved and released in water, so that the reaction rate of H + ions in rocks is greatly reduced; urea nitrate and urea phosphate are chemically decomposed to provide effective NO3 < - >, PO43 < - >, and the acid liquor blockage removal performance is promoted to be improved through the ion synergistic effect; the ammonium bifluoride and the ammonium fluoroborate improve the solubility of the working solution to silicate minerals such as feldspar in sandstone by ionizing F-ions. The ionic equilibrium in the chemical reaction of reactants is involved, and the effective ion concentration is slowly released, so that the slow release rate and the slow speed of the solid chelating acid working solution are further delayed. Under the condition of certain construction displacement, the working fluid can play a longer action distance in the reservoir. Meanwhile, the initial plugging removal capability of the working fluid is also relative to that of the conventional acidizing fluid, so that excessive corrosion of a near well bore is avoided. The 2,3,7, 9-tetramethyl-5-decyne-4, 7-diol polyoxyethylene ether has excellent interfacial tension reducing performance and permeability, reduces the emulsion blockage of the working solution, and improves the sweep performance of the working solution. The tropane oil-based hydroxyethyl imidazoline inhibits the corrosion of the working solution to metal, and avoids the introduction of extra Fe3+ in the working solution; the tropane oil-based hydroxyethyl imidazoline, the isoascorbic acid and the nitrilotriacetic acid can chelate free Fe3+ in the solution, so that the formation of acid sludge is reduced, and the damage of working solution to a reservoir is reduced. The stearic acid and Span-60 have the tasks of wrapping and bonding the solid chelating acid, improving the solid form of the chelating acid, being capable of synergistically slowing down the speed of the working solution, being in a liquid state at a certain temperature (60 ℃ and above), and not additionally increasing the damage of a reservoir stratum.
The results of the comparative experiment of the solid chelating acid for water injection well augmented injection prepared by the embodiment of the invention are as follows: (the product of example 4 was used here, and the effects of the other examples were substantially the same as those of example 4)
(1) The comparison of the retarding performance of the solid chelated acid for increasing the injection of the water injection well and the earthy acid shows that when the concentration of the residual acid is reduced to a half (7.5%), the time required by the earthy acid is 8.5min, the time required by the solid chelated acid with 40 meshes is 36.1min, and the time required by the solid chelated acid with 20 meshes is 48.7min, which indicates that the retarding performance of the solid chelated acid with 20 meshes to 40 meshes is 4 to 6 times of that of the earthy acid system.
(2) The corrosion performance results of the solid chelate acid used for injection enhancement of the water injection well show (see table 1), that at 50 ℃, the solid chelate acid is extremely low at 0.002 g/(m2 h), and the corrosion rate increases with increasing temperature, but compared with the earth acid, the corrosion rate of the solid chelate acid to the metal is one fifth of that of the earth acid to the metal.
TABLE 1 solid chelated acid corrosion Performance test for water injection well stimulation
The parts of the process not described in detail in this embodiment are common knowledge in the industry, and are not described here. The reagents involved are all available directly from the market.
Claims (4)
1. A solid chelating acid for increasing injection of a water injection well is characterized in that: the material comprises the following raw materials in percentage by weight: 30-40% of main agent, 20-30% of auxiliary agent, 10-15% of reinforcing agent, 3-8% of active agent, 2-3% of inhibitor, 5-10% of stabilizer and 15-30% of adhesive; the main agent consists of one or two of hydrazine hydrochloride and hydrazine dihydrochloride, sulfamic acid and hydroxyethylidene diphosphonic acid, and the weight percentage of the main agent is 30-40 percent: 10-15% of one or two of hydrazine hydrochloride and hydrazine dihydrochloride, 10-12% of sulfamic acid and 10-13% of hydroxyethylidene diphosphonic acid; the auxiliary agent consists of urea nitrate and urea phosphate, wherein the weight percentage of the auxiliary agent is 20-30%, the weight percentage of the urea nitrate is 15-20%, and the weight percentage of the urea phosphate is 5-10%; the reinforcing agent consists of ammonium bifluoride and ammonium fluoroborate, wherein in the reinforcing agent with the weight percentage of 10-15%, the weight percentage of the ammonium bifluoride is 5-7%, and the weight percentage of the ammonium fluoroborate is 5-8%; the active agent is 2,3,7, 9-tetramethyl-5-decyne-4, 7-diol polyoxyethylene ether; the inhibitor is tropyl hydroxyethyl imidazoline; the stabilizer consists of 5-10 wt% of isoascorbic acid and 2-4 wt% of nitrilotriacetic acid.
2. The solid chelating acid for the injection enhancement of a water injection well as defined in claim 1, wherein the binder is composed of 15-30% by weight of stearic acid 1801 and Span-60, wherein the stearic acid 1801 accounts for 10-20% by weight of the binder, and the Span-60 accounts for 5-10% by weight of the binder.
3. The method for preparing the solid chelating acid for the augmented injection of the water injection well according to the claim 1 is characterized by comprising the following steps:
step 1), preparing materials, weighing the raw materials of the solid chelating acid for increasing injection of the water injection well according to the formula:
30-40% of main agent, 20-30% of auxiliary agent, 10-15% of reinforcing agent, 3-8% of active agent, 2-3% of inhibitor, 5-10% of stabilizer and 15-30% of adhesive;
step 2) grinding the adhesive with the formula amount by a grinder under the protection of liquid nitrogen until the adhesive passes through 100 meshes to obtain powder for later use;
step 3) raising the temperature in the kneader, controlling the constant temperature at 40-42 ℃, adding the main agent with the formula amount, and stirring for 20-30 min; adding inhibitor, enhancer and adjuvant, and stirring for 30-50 min;
step 4) cooling the mixture obtained in the step 3), sieving the mixture by using a 30-50-mesh sieve, and continuously kneading the mixture which does not pass through the sieve in a kneader until the mixture completely passes through the 30-50-mesh sieve; adding the mixture passing through the screen into the kneader again, controlling the constant temperature at 50-52 ℃, adding the active agent and the stabilizing agent according to the formula amount, and stirring for 20-30 min;
step 5) slowly adding the ground powder in the step 2) into the mixture mixed in the step 4), and stirring for 20-30 min; and (3) closing the kneader, continuing stirring for 20-30min, sieving by using a 20-40 mesh sieve, and continuing kneading without passing through the sieve until all the solid chelate acid passes through the 20-40 mesh sieve, namely the solid chelate acid for increasing injection of the water injection well.
4. The method for preparing the solid chelating acid for the augmented injection of the water injection well according to the claim 3, is characterized in that: the main agent consists of one or two of hydrazine hydrochloride and hydrazine dihydrochloride, sulfamic acid and hydroxyethylidene diphosphonic acid, and the weight percentage of the main agent is 30-40 percent: 10-15% of one or two of hydrazine hydrochloride and hydrazine dihydrochloride, 10-12% of sulfamic acid and 10-13% of hydroxyethylidene diphosphonic acid; the auxiliary agent consists of urea nitrate and urea phosphate, wherein the weight percentage of the auxiliary agent is 20-30%, the weight percentage of the urea nitrate is 15-20%, and the weight percentage of the urea phosphate is 5-10%; the reinforcing agent consists of ammonium bifluoride and ammonium fluoroborate, wherein in the reinforcing agent with the weight percentage of 10-15%, the weight percentage of the ammonium bifluoride is 5-7%, and the weight percentage of the ammonium fluoroborate is 5-8%; the active agent is 2,3,7, 9-tetramethyl-5-decyne-4, 7-diol polyoxyethylene ether; the inhibitor is tropyl hydroxyethyl imidazoline; the stabilizer consists of 5-10 wt% of isoascorbic acid and 2-4 wt% of nitrilotriacetic acid, wherein the isoascorbic acid accounts for 3-6 wt% of the stabilizer; the adhesive consists of 15-30 wt% of stearic acid 1801 and Span-60, wherein the stearic acid 1801 accounts for 10-20 wt% and the Span-60 accounts for 5-10 wt%.
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| CN103484088A (en) * | 2013-09-06 | 2014-01-01 | 廊坊中石油科学技术研究院 | Blocking remover suitable for acidification of complex lithologic reservoirs and acidification blocking removing method |
| WO2016036555A1 (en) * | 2014-09-04 | 2016-03-10 | Ideal Energy Solutions IP Control, LLC | Aqueous cleaning composition and method |
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| CN103484088A (en) * | 2013-09-06 | 2014-01-01 | 廊坊中石油科学技术研究院 | Blocking remover suitable for acidification of complex lithologic reservoirs and acidification blocking removing method |
| WO2016036555A1 (en) * | 2014-09-04 | 2016-03-10 | Ideal Energy Solutions IP Control, LLC | Aqueous cleaning composition and method |
| CN106281273A (en) * | 2015-05-15 | 2017-01-04 | 中国石油天然气股份有限公司 | Acid liquor system for acidifying carbonate reservoir |
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