CN109021950A - A kind of solid chelated acid and preparation method thereof for water injection well stimulation - Google Patents
A kind of solid chelated acid and preparation method thereof for water injection well stimulation Download PDFInfo
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- 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
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- 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
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Abstract
The solid chelated acid and preparation method thereof that the invention discloses a kind of for water injection well stimulation, it is related to water injection well in oil fields increasing injection technical field, which is to be composed of the following weight percentages of raw materials: host agent 30-40%, adjuvant 20-30%, reinforcing agent 10-15%, activating agent 3-8%, inhibitor 2-3%, stabilizer are 5-10% and adhesive is 15-30%.Transport in acidification de-plugging can be reduced using the present invention, stored, the safety and environmental protection hidden danger in use process, acid solution sustained release rate is greatly improved, expand plug removal radius, be conducive to water injection well removing clog in deep reservoir, it is efficient to improve the measure of water injection well increasing injection.
Description
Technical field
The present invention relates to a kind of solid chelated acid, in particular to a kind of solid chelated acid and its system for water injection well stimulation
Preparation Method.Belong to water injection well in oil fields increasing injection technical field.
Background technique
With the extension of oil field development time, due to the reduction of stratum energy, oil well output decline needs waterflooding extraction to tie up
Hold stratum energy.In waterflooding extraction, since the factors such as particles in injected water, fouling and bacterial corrosion product block, water filling
Well is presented high pressure and shorts.Water injection well needs to carry out de-plugging operation, and currently used de-plugging agent is acid solution composition, and acid solution belongs to danger
Dangerous chemicals, acid solution in transport, storage, use process there are environmental protection hidden danger and acid solution to metal erosion security risk；Together
When acid solution and reservoir Minerals reaction speed it is fast, it is small that there are plug removal radius, leads to the nearly excessive corrosion of pit shaft, and removing clog in deep reservoir is limited
Problem.As new environmental law is implemented and safe production act regulatory requirements, therefore it is acidified de-plugging and needs to follow up technology growth requirement,
Develop it is a kind of conducive to acid solution in transport, storage, the de-plugging product used.
In addition, China Patent No. " CN102775980A ", discloses on November 11st, 2012 a kind of suitable for complex lithology
Reservoir Acidization de-plugging agent.Its component and proportion are as follows by weight percentage: hydrochloric acid 0~12%, ammonium acid fluoride 0%~3%, amino sulphur
Sour 0%~10%, fluoboric acid 0%~5%, boric acid 0%~3%, ethyl alcohol 0~4%, triethanolamine 0~2%, glacial acetic acid 3%, corrosion inhibiter 4.0
~6.0%, mutual solvent 2.0~4.0%, bleeding agent 0.5~1.0%, clay stabilizer 2.0%, water 45~88.5%.Mainly solve
For oil field lithology, physical difference is larger and is interspersed and asks using conventional waterflooding well acidizing de-plugging construction effect is undesirable
Topic.Should be suitable for complex lithology reservoir acidification blocking remover, can either effectively corrosion subterranean minerals and tamper, and do not destroy rock stratum
Skeleton can prevent the generation of secondary precipitation caused by sensitive minerals, improve oil reservoir water absorbing capacity, increase average single well measure and increase day by day
Water injection rate.China Patent No. " CN104194759A ", on December 10th, 2014 disclose a kind of oil extraction in oil field stratum neutrality de-plugging
Agent composition is made of following portions by weight raw material: 30~36 parts of polyepoxy sodium succinate, gathers 18~25 parts of sodium gluconate
2~3 parts of ethylene glycol, 2~4 parts of triethanolamine, 9~12 parts of ethyl lactate, 7~10 parts of sodium sulfate of polyethenoxy ether of fatty alcohol, ammonia
8~12 parts of base acid sodium, 10~15 parts of active attapulgite, 0.1~0.2 part of vanadic anhydride, 5~7 parts of lipase, sorbitol anhydride
5~8 parts of aliphatic ester, to 15~18 parts of hydroxyl sulfoacid sodium, 3~7 parts of t-butyl hydroperoxide and double ethylene glycol laurates 0.1
~0.3 part.De-plugging speed of the present invention is fast, neutral material that is corrosion-free, can quickly dissolving ternary composite displacement system generation is dirty, pitch
Deposit dirt, carbonate scale, silicate scale etc., de-plugging waste liquid can self-degradation, without the row of returning ground carry out sewage treatment, cleaning oil
Field removal of bridge formation has corrosion-free, no dead angle, does not generate precipitating and secondary stifled well, and de-plugging handled the time no more than 24 hours.
Using above-mentioned patent as the de-plugging product of representative, the compound carry out de-plugging of the acid solution of mainly liquid or solid complexing
Agent passes through complex reaction de-plugging.Safety and environmental protection hidden danger of the acid solution in transport, storage, use process is larger, because reaction is led fastly
Cause plug removal radius small；Although solid complexing agent avoids the transport of liquid acid solution, storage disadvantage, but there are de-plugging scarce capacities
Problem, at the same it is poor to the specific aim of water injection well tamper.For water injection well in oil fields block releasing technique in order to adapt to new environmental law requirement, having must
Research and develop a kind of solid chelating acid product, especially low-permeability oil deposit water injection well increasing injection that can preferably solve problem above
Demand.
Summary of the invention
The solid chelated acid and preparation method thereof that the object of the present invention is to provide a kind of for water injection well stimulation, the present invention gram
Safety and environmental protection problem of the conventional acid solution in transport, storage and use process is taken, while solving conventional acidulation there are acid liquid reactions
Rate is fast, and plug removal radius is small, and the nearly excessive corrosion of pit shaft, nearly pit shaft shakes out seriously after measure, and service shaft validity period is short, causes to fill the water
The problem of well measure is frequent, increases oil field development cost.Solid chelated acid provided by the invention is solid state, is not connect with water
Touch it is corrosion-free, without hazardous chemical tank special-purpose vehicle transport, storage and it is easy to use；Solid chelated acid provided by the invention is prepared
After solution, generation acid solution need to be ionized, slows down the sustained release rate of acid solution, retardative property improves, and expands plug removal radius, it can be achieved that right
The blocking of water injection well deep carries out de-plugging, improves measure effective percentage and extends measure validity period.
To achieve the above object, the technical solution adopted by the present invention is that: a kind of solid chelated acid for water injection well stimulation,
It is characterized by: it is to be composed of the following weight percentages of raw materials: host agent 30-40%, adjuvant 20-30%, reinforcing agent are
10-15%, activating agent 3-8%, inhibitor 2-3%, stabilizer are 5-10% and adhesive is 15-30%.
The host agent is by one or two, sulfamic acid, hydroxy ethylene diphosphonic acid in hydrazine hydrochloride and double hydrazine hydrochlorides
Composition, weight percent is in the host agent of 30-40%: one or two kinds of weight percent is 10- in hydrazine hydrochloride and double hydrazine hydrochlorides
15%, the weight percent of sulfamic acid is 10-12%, and the weight percent of hydroxy ethylene diphosphonic acid is 10-13%, wherein hydroxyl
The mass percentage content of base ethylidene diphosphonic acid is 90%.
The adjuvant is made of urea nitrate and urea phosphate, weight percent be 20-30% adjuvant in, urea nitrate
Weight percent is 15-20%, and the weight percent of urea phosphate is 5-10%.
The reinforcing agent is made of ammonium acid fluoride and ammonium fluoroborate, weight percent be 10-15% reinforcing agent in,
The weight percent of ammonium acid fluoride is 5-7%, and the weight percent of ammonium fluoroborate is 5-8%.
The activating agent is -5 decine -4,7- glycol polyoxyethylene ether of 2,3,7,9- tetramethyl.
The inhibitor is capper's oil base hydroxyethyl imidazole quinoline.
The stabilizer is made of arabo-ascorbic acid and nitrilotriacetic acid, and weight percent is the stabilizer of 5-10%
In, the weight percent of arabo-ascorbic acid is 3-6%, and the weight percent of nitrilotriacetic acid is 2-4%.
The adhesive is made of stearic acid 1801 and Span-60, weight percent be 15-30% adhesive in,
The weight percent of stearic acid 1801 is 10-20%, and the weight percent of Span-60 is 5-10%.
A kind of preparation method of the solid chelated acid for water injection well stimulation, it is characterised in that steps are as follows:
Step 1) stock, the raw material of the solid chelated acid for water injection well stimulation is weighed by formula ratio:
Host agent is 30-40%, adjuvant 20-30%, reinforcing agent 10-15%, activating agent 3-8%, inhibitor 2-3%, stabilizer
It is 15-30% for 5-10% and adhesive；
The adhesive of formula ratio is ground to grinder through 100 mesh by step 2 under conditions of protection of liquid nitrogen, obtains powder, to
With；
Step 3) will mediate built-in temperature and increase and control constant temperature in 40-42 DEG C, and the host agent of formula ratio is added, and stir 20-
30min；The inhibitor of formula ratio is added, the reinforcing agent and adjuvant of formula ratio are added immediately, stirs 30-50min；
Step 4) is cooling by the mixture of step 3), is sieved with 30-50 mesh screen, is not mediated in kneader by the continuation of sieve
To all passing through 30-50 mesh screen；The mixture for crossing sieve is added again in kneader and controls constant temperature in 50-52 DEG C, is added
Enter the activating agent and stabilizer of formula ratio, stirs 20-30min；
The powder of the grinding of step 2 is slowly added into the mixture that step 4) mixes by step 5), stirs 20-30min；
Kneader temperature is closed, continues to stir 20-30min, is sieved with 20-40 mesh screen, does not continue to mediate to all logical by what is sieved
20-40 mesh screen is crossed, that is, is used for the solid chelated acid of water injection well stimulation.
The host agent is by one or two, sulfamic acid, hydroxy ethylene diphosphonic acid in hydrazine hydrochloride and double hydrazine hydrochlorides
Composition, weight percent is in the host agent of 30-40%: one or two kinds of weight percent is 10- in hydrazine hydrochloride and double hydrazine hydrochlorides
15%, the weight percent of sulfamic acid is 10-12%, and the weight percent of hydroxy ethylene diphosphonic acid is 10-13%；Described
Adjuvant is made of urea nitrate and urea phosphate, and weight percent is in the adjuvant of 20-30%, and the weight percent of urea nitrate is 15-
20%, the weight percent of urea phosphate is 5-10%；The reinforcing agent is made of ammonium acid fluoride and ammonium fluoroborate, weight percent
Than in the reinforcing agent for 10-15%, the weight percent of ammonium acid fluoride is 5-7%, the weight percent of ammonium fluoroborate is 5-8%；Institute
The activating agent stated is -5 decine -4,7- glycol polyoxyethylene ether of 2,3,7,9- tetramethyl；The inhibitor is capper's oil base hydroxyl
Ethyl imidazol(e) quinoline；The stabilizer is made of arabo-ascorbic acid and nitrilotriacetic acid, and weight percent is the stabilization of 5-10%
In agent, the weight percent of arabo-ascorbic acid is 3-6%, and the weight percent of nitrilotriacetic acid is 2-4%；The adhesive is
It is made of stearic acid 1801 and Span-60, weight percent is the weight percent of stearic acid 1801 in the adhesive of 15-30%
For 10-20%, the weight percent of Span-60 is 5-10%.
Compared with prior art, advantages of the present invention is as follows:
1, in the safety and environmental protection problem in the transport of material, storage and use process, solid chelated acid is than conventional acidulation de-plugging
Liquid oil conspicuousness improves.
Transport aspect: solid chelated acid is solid particle, and self-corrosion is small, can be transported with heavy-duty bag by truck
It is defeated；Conventional acidulation blockages relieving fluid needs extraordinary dangerous material tank car transport.
In terms of storage: solid chelated acid is stored by chemical balance motion, and conventional acidifying unblocking liquid need to be by hazardous chemical
Management storage.
Use aspect: solid chelated acid is directly added into acid solution tank or mixing sand tank, effective by slow release in flow process
Ingredient, no acidic gas release are minimum to injection device and the corrosion of water injection pipe string；Exist in conventional acidulation blockages relieving fluid use a large amount of
Sour gas release, it is acid strong, it is serious to metal equipment corrosion.
With conventional acid liquid phase ratio, solid chelated acid greatly reduces the cost in transport, storage and use process.
2, solid chelated acid improves de-plugging working solution sustained release rate, slow rate, expands plug removal radius, overcomes nearly pit shaft mistake
Corrosion phenomenon is spent, is conducive to the blocking of water injection well deep and carries out de-plugging.
Hydrazine hydrochloride, double hydrazine hydrochlorides, sulfamic acid and hydroxy ethylene diphosphonic acid are solid acid in the present invention, are added to the water
It is slowly dissolved, discharges H+ ion, H+ ion reaction rate in rock will substantially reduce；Urea nitrate and urea phosphate are through chemistry point
Solution, provides effective NO3-, PO43-, by ion synergistic effect, acid solution de-plugging performance is promoted to improve；Ammonium acid fluoride and fluoboric acid
Ammonium improves working solution to the solubility property of the silicate minerals such as sandstone andesine by ionization F- ion.It all refers to react above
Ionization equilibrium in the chemical reaction of object, slow release effective ion concentration, to further delay solid chelated acid working solution
Sustained release rate, slow rate.Under conditions of operational discharge capacity is certain, working solution will play farther operating distance in reservoir.Simultaneously
The de-plugging ability at working solution initial stage also relatively conventional acidifying solution, avoids the nearly excessive corrosion of pit shaft.- 5 last of the ten Heavenly stems of 2,3,7,9- tetramethyl
Alkynes -4,7- glycol polyoxyethylene ether has excellent drop interfacial tension performance and permeability, reduces working solution emulsion plugging, improves
Working solution involves performance.Capper's oil base hydroxyethyl imidazole quinoline inhibits working solution to metal erosion, avoids additional in working solution
The introducing of Fe3+；The Fe3 that capper's oil base hydroxyethyl imidazole quinoline, arabo-ascorbic acid and nitrilotriacetic acid can dissociate in chelate solution
+, the formation of acid sludge is reduced, reduces working solution to reservoir damage.Stearic acid and Span-60 its task are package, bonding solid chela
Acid is closed, the solid forms of chelated acid is improved, can cooperate with and slow down working solution retardative property, at a certain temperature (at 60 DEG C or more)
Liquid is presented, will not additionally increase the injury of reservoir.
Detailed description of the invention
Below in conjunction with specification drawings and specific embodiments, the present invention is described in further detail:
Fig. 1 is solid chelated acid and mud acid slow contrast schematic diagram (60 DEG C) of the present invention for water injection well stimulation.
Specific embodiment
Embodiment 1
The invention discloses a kind of solid chelated acids for water injection well stimulation, it is the raw material group by following weight percentage
At: host agent 30-40%, adjuvant 20-30%, reinforcing agent 10-15%, activating agent 3-8%, inhibitor 2-3%, stabilizer
It is 15-30% for 5-10% and adhesive.
The solid chelated acid of water injection well stimulation is prepared using heating, the kneading in this field.
Specific step is as follows for a kind of preparation method of the solid chelated acid for water injection well stimulation:
Step 1) stock, the raw material of the solid chelated acid for water injection well stimulation is weighed by formula ratio:
Host agent is 30-40%, adjuvant 20-30%, reinforcing agent 10-15%, activating agent 3-8%, inhibitor 2-3%, stabilizer
It is 15-30% for 5-10% and adhesive；
The adhesive of formula ratio is ground to grinder through 100 mesh by step 2 under conditions of protection of liquid nitrogen, obtains powder, to
With；
Step 3) will mediate built-in temperature and increase and control constant temperature in 40-42 DEG C, and the host agent of formula ratio is added, and stir 20-
30min；The inhibitor of formula ratio is added, the reinforcing agent of formula ratio and the adjuvant of formula ratio are added immediately, stirs 30-50min；
Step 4) is cooling by the mixture of step 3), is sieved with 30-50 mesh screen, is not mediated in kneader by the continuation of sieve
To all passing through 30-50 mesh screen；The mixture for crossing sieve is added again in kneader and controls constant temperature in 50-52 DEG C, is added
Enter the activating agent of formula ratio and the stabilizer of formula ratio, stirs 20-30min；
The powder of the grinding of step 2 is slowly added into the mixture that step 4) mixes by step 5), stirs 20-30min；
Kneader temperature is closed, continues to stir 20-30min, is sieved with 20-40 mesh screen, does not continue to mediate to all logical by what is sieved
20-40 mesh screen is crossed, that is, is used for the solid chelated acid of water injection well stimulation.
The present invention reduces transport in acidification de-plugging for the solid chelated acid of water injection well stimulation, stores, in use process
Safety and environmental protection hidden danger, greatly improve acid solution sustained release rate, expand plug removal radius, be conducive to water injection well removing clog in deep reservoir.
Embodiment 2
On the basis of embodiment 1, the host agent is by one or two, sulfamic acid, hydroxyl in hydrazine hydrochloride and double hydrazine hydrochlorides
Base ethylidene diphosphonic acid composition, weight percent are in the host agent of 30-40%: one or two kinds of in hydrazine hydrochloride and double hydrazine hydrochlorides
Weight percent is 10-15%, and the weight percent of sulfamic acid is 10-12%, the weight percent of hydroxy ethylene diphosphonic acid
For 10-13%, wherein the mass percentage content of hydroxy ethylene diphosphonic acid is 90%.The adjuvant is by urea nitrate and phosphorus
Sour urea composition, weight percent are in the adjuvant of 20-30%, and the weight percent of urea nitrate is 15-20%, the weight hundred of urea phosphate
Divide than being 5-10%.The reinforcing agent is made of ammonium acid fluoride and ammonium fluoroborate, and weight percent is the reinforcing agent of 10-15%
In, the weight percent of ammonium acid fluoride is 5-7%, and the weight percent of ammonium fluoroborate is 5-8%.The activating agent is 2,3,7,
- 5 decine -4,7- glycol polyoxyethylene ether of 9- tetramethyl.The inhibitor is capper's oil base hydroxyethyl imidazole quinoline.Described is steady
Determine agent to be made of arabo-ascorbic acid and nitrilotriacetic acid, weight percent is the weight of arabo-ascorbic acid in the stabilizer of 5-10%
Amount percentage is 3-6%, and the weight percent of nitrilotriacetic acid is 2-4%.The adhesive is by stearic acid 1801 and Span-
60 compositions, weight percent are in the adhesive of 15-30%, and the weight percent of stearic acid 1801 is 10-20%, Span-60's
Weight percent is 5-10%.
Embodiment 3
Specific step is as follows for a kind of preparation method of the solid chelated acid for water injection well stimulation:
Step 1) stock, the raw material of the solid chelated acid for water injection well stimulation is weighed by formula ratio:
Host agent is 30-40%, adjuvant 20-30%, reinforcing agent 10-15%, activating agent 3-8%, inhibitor 2-3%, stabilizer
It is 15-30% for 5-10% and adhesive；The host agent be by one or two in hydrazine hydrochloride and double hydrazine hydrochlorides, sulfamic acid,
Hydroxy ethylene diphosphonic acid composition, weight percent are in the host agent of 30-40%: one or two kinds of in hydrazine hydrochloride and double hydrazine hydrochlorides
Weight percent be 10-15%, the weight percent of sulfamic acid is 10-12%, the weight percent of hydroxy ethylene diphosphonic acid
Than for 10-13%；The adjuvant is made of urea nitrate and urea phosphate, and weight percent is urea nitrate in the adjuvant of 20-30%
Weight percent be 15-20%, the weight percent of urea phosphate is 5-10%；The reinforcing agent is by ammonium acid fluoride and fluorine boron
Sour ammonium composition, weight percent are in the reinforcing agent of 10-15%, and the weight percent of ammonium acid fluoride is 5-7%, the weight of ammonium fluoroborate
Amount percentage is 5-8%；The activating agent is -5 decine -4,7- glycol polyoxyethylene ether of 2,3,7,9- tetramethyl；The suppression
Preparation is capper's oil base hydroxyethyl imidazole quinoline；The stabilizer is made of arabo-ascorbic acid and nitrilotriacetic acid, weight hundred
Divide in the stabilizer than being 5-10%, the weight percent of arabo-ascorbic acid is 3-6%, and the weight percent of nitrilotriacetic acid is 2-
4%；The adhesive is made of stearic acid 1801 and Span-60, and weight percent is tristearin in the adhesive of 15-30%
The weight percent of acid 1801 is 10-20%, and the weight percent of Span-60 is 5-10%.
The stearic acid of formula ratio 1801 and Span-60 are ground to grinder logical by step 2 under conditions of protection of liquid nitrogen
100 mesh are crossed, obtain powder, for use；
Step 3) increases by built-in temperature is mediated and controls constant temperature in 40-42 DEG C, and hydrazine hydrochloride (or double hydrochloric acid of formula ratio are added
The mixture that hydrazine or hydrazine hydrochloride and double hydrazine hydrochlorides mixs by weight 1:1), sulfamic acid, hydroxy ethylene diphosphonic acid, stir
20-30min；Capper's oil base hydroxyethyl imidazole quinoline of formula ratio is added, the ammonium acid fluoride and fluoboric acid of formula ratio are added immediately
The urea nitrate and urea phosphate of ammonium and formula ratio stir 30-50min；
Step 4) is cooling by the mixture of step 3), is sieved with 30-50 mesh screen, is not mediated in kneader by the continuation of sieve
To all passing through 30-50 mesh screen；The mixture for crossing sieve is added again in kneader and controls constant temperature in 50-52 DEG C, is added
Enter the arabo-ascorbic acid and nitrilo three of 2,3,7,9- tetramethyl -5 decine -4,7- glycol polyoxyethylene ether and formula ratio of formula ratio
Acetic acid stirs 20-30min；
The powder of whole stearic acid 1801 of the grinding of step 2 and Span-60 is slowly added into step 4) and mixed by step 5)
Mixture in, stir 20-30min；Kneader temperature is closed, continues to stir 20-30min, is sieved with 20-40 mesh screen, not
Continue to mediate to all by 20-40 mesh screen by sieve, that is, is used for the solid chelated acid of water injection well stimulation.
Embodiment 4
It is hard by 18% under conditions of protection of liquid nitrogen according to weight percent meter in the solid chelated acid for occupying water injection well stimulation
Resin acid 1801 and 10%Span-60 are ground to by 100 mesh, for use with grinder.Built-in temperature will be mediated first to increase and control
In 42 DEG C 5% hydrazine hydrochloride, 5% pair of hydrazine hydrochloride, 10% sulfamic acid and 12% hydroxy ethylene diphosphonic acid is added, wherein hydroxyl in constant temperature
The mass percentage content of ethylidene diphosphonic acid is 90%, stirs 30min；2% capper's oil base hydroxyethyl imidazole quinoline is added, immediately
5% ammonium acid fluoride, 5% ammonium fluoroborate, 15% urea nitrate and 5% urea phosphate is added, stirs 50min；Mixture is cooling, with 50 meshes
Net sieving does not continue to mediate to all by 50 mesh screens by what is sieved；Feed the mixture into kneader and control constant temperature in
52 DEG C, -5 decine -4,7- glycol polyoxyethylene ether of 3%2,3,7,9- tetramethyl, three second of 3% arabo-ascorbic acid and 2% nitrilo is added
Acid stirs 30min；It is slowly added to stearic acid 1801 and Span-60 powder whole after grinding, stirs 30min；Close kneader
Temperature, continue stir 30min, with 40 mesh screens be sieved, by sieve continue mediate to all by 40 mesh screens to get with
Acid product is chelated in the solid of water injection well stimulation.
Embodiment 5
It is hard by 10% under conditions of protection of liquid nitrogen according to weight percent meter in the solid chelated acid for occupying water injection well stimulation
Resin acid 1801 and 5%Span-60 are ground to by 100 mesh, for use with grinder.Built-in temperature will be mediated first to increase and control
In 40 DEG C 10% pair of hydrazine hydrochloride, 10% sulfamic acid and 10% hydroxy ethylene diphosphonic acid is added, wherein hydroxy ethylene two in constant temperature
The mass percentage content of phosphonic acids is 90%, stirs 20min；2% capper's oil base hydroxyethyl imidazole quinoline is added, 7% fluorine is added immediately
Change hydrogen ammonium, 8% ammonium fluoroborate, 15% urea nitrate and 10% urea phosphate, stirs 30min；Mixture is cooling, it is sieved with 30 mesh screens,
Do not continue to mediate to all by 30 mesh screens by what is sieved；It feeds the mixture into kneader and controls constant temperature in 50 DEG C, add
Enter -5 decine -4,7- glycol polyoxyethylene ether of 6%2,3,7,9- tetramethyl, 3% arabo-ascorbic acid and 4% nitrilotriacetic acid, stirs
20min；It is slowly added to stearic acid 1801 and Span-60 powder whole after grinding, stirs 20min；Kneader temperature is closed, after
Continuous stirring 20min, is sieved with 20 mesh screens, does not continue to mediate to all by 20 mesh screens to get for filling the water by what is sieved
The solid of well augmented injection chelates acid product.
Embodiment 6
It is hard by 13% under conditions of protection of liquid nitrogen according to weight percent meter in the solid chelated acid for occupying water injection well stimulation
Resin acid 1801 and 7%Span-60 are ground to by 100 mesh, for use with grinder.Built-in temperature will be mediated first to increase and control
In 41 DEG C 11% pair of hydrazine hydrochloride, 11% sulfamic acid and 11% hydroxy ethylene diphosphonic acid is added, wherein hydroxy ethylene two in constant temperature
The mass percentage content of phosphonic acids is 90%, stirs 25min；3% capper's oil base hydroxyethyl imidazole quinoline is added, 6% fluorine is added immediately
Change hydrogen ammonium, 6% ammonium fluoroborate, 16% urea nitrate and 6% urea phosphate, stirs 40min；Mixture is cooling, it is sieved with 40 mesh screens,
Do not continue to mediate to all by 40 mesh screens by what is sieved；It feeds the mixture into kneader and controls constant temperature in 51 DEG C, add
Enter -5 decine -4,7- glycol polyoxyethylene ether of 4%2,3,7,9- tetramethyl, 3% arabo-ascorbic acid and 3% nitrilotriacetic acid, stirs
25min；It is slowly added to stearic acid 1801 and Span-60 powder whole after grinding, stirs 25min；Kneader temperature is closed, after
Continuous stirring 25min, is sieved with 30 mesh screens, does not continue to mediate to all by 30 mesh screens to get for filling the water by what is sieved
The solid of well augmented injection chelates acid product.
Hydrazine hydrochloride, double hydrazine hydrochlorides, sulfamic acid and hydroxy ethylene diphosphonic acid are solid acid in the present invention, are added to the water
It is slowly dissolved, discharges H+ ion, H+ ion reaction rate in rock will substantially reduce；Urea nitrate and urea phosphate are through chemistry point
Solution, provides effective NO3-, PO43-, by ion synergistic effect, acid solution de-plugging performance is promoted to improve；Ammonium acid fluoride and fluoboric acid
Ammonium improves working solution to the solubility property of the silicate minerals such as sandstone andesine by ionization F- ion.It all refers to react above
Ionization equilibrium in the chemical reaction of object, slow release effective ion concentration, to further delay solid chelated acid working solution
Sustained release rate, slow rate.Under conditions of operational discharge capacity is certain, working solution will play farther operating distance in reservoir.Simultaneously
The de-plugging ability at working solution initial stage also relatively conventional acidifying solution, avoids the nearly excessive corrosion of pit shaft.- 5 last of the ten Heavenly stems of 2,3,7,9- tetramethyl
Alkynes -4,7- glycol polyoxyethylene ether has excellent drop interfacial tension performance and permeability, reduces working solution emulsion plugging, improves
Working solution involves performance.Capper's oil base hydroxyethyl imidazole quinoline inhibits working solution to metal erosion, avoids additional in working solution
The introducing of Fe3+；The Fe3 that capper's oil base hydroxyethyl imidazole quinoline, arabo-ascorbic acid and nitrilotriacetic acid can dissociate in chelate solution
+, the formation of acid sludge is reduced, reduces working solution to reservoir damage.Stearic acid and Span-60 its task are package, bonding solid chela
Acid is closed, the solid forms of chelated acid is improved, can cooperate with and slow down working solution retardative property, at a certain temperature (at 60 DEG C or more)
Liquid is presented, will not additionally increase the injury of reservoir.
It is as follows that the solid chelated acid for being used for water injection well stimulation that the embodiment of the present invention is prepared is compared into experimental result:
(here using the product of embodiment 4, using the almost the same of other embodiments effect and embodiment 4)
(1) for the solid chelated acid of water injection well stimulation and mud acid retardative property comparison display (see figure 1), when residual acid concentration reduces
When to half (7.5%), the time needed for mud acid is 8.5min, and the time needed for 40 mesh solid chelated acids is 36.1min, 20 mesh
Time needed for solid chelated acid is 48.7min, illustrates that 20-40 mesh solid chelated acid retardative property is 4-6 times of mud acid system.
(2) for the corrosive nature (see Table 1) as the result is shown of the solid chelated acid of water injection well stimulation, at 50 DEG C, solid
Extremely low chelated acid is 0.002 g/ (m2h), is increased with temperature, and corrosion rate increases, but compared with mud acid, solid chelated acid pair
Corrosion of metal rate is mud acid to 1/5th of corrosion of metal rate.
Solid chelated acid corrosive nature of the table 1 for water injection well stimulation is tested
The process part that the present embodiment does not describe in detail adheres to the common knowledge of the industry separately, does not describe one by one here.It is related
Reagent can directly be bought from market.
Claims (10)
1. a kind of solid chelated acid for water injection well stimulation, it is characterised in that: it is the raw material group by following weight percentage
At: host agent 30-40%, adjuvant 20-30%, reinforcing agent 10-15%, activating agent 3-8%, inhibitor 2-3%, stabilizer
It is 15-30% for 5-10% and adhesive.
2. a kind of solid chelated acid for water injection well stimulation according to claim 1, it is characterised in that: the master
Agent is made of one or two, sulfamic acid, hydroxy ethylene diphosphonic acid in hydrazine hydrochloride and double hydrazine hydrochlorides, and weight percent is
In the host agent of 30-40%: one or two kinds of weight percent is 10-15%, the weight of sulfamic acid in hydrazine hydrochloride and double hydrazine hydrochlorides
Amount percentage is 10-12%, and the weight percent of hydroxy ethylene diphosphonic acid is 10-13%, wherein hydroxy ethylene diphosphonic acid
Mass percentage content is 90%.
3. a kind of solid chelated acid for water injection well stimulation according to claim 1, it is characterised in that: the adjuvant
It being made of urea nitrate and urea phosphate, weight percent is in the adjuvant of 20-30%, and the weight percent of urea nitrate is 15-20%,
The weight percent of urea phosphate is 5-10%.
4. a kind of solid chelated acid for water injection well stimulation according to claim 1, it is characterised in that: the increasing
Strong agent is made of ammonium acid fluoride and ammonium fluoroborate, and weight percent is the weight hundred of ammonium acid fluoride in the reinforcing agent of 10-15%
Divide than being 5-7%, the weight percent of ammonium fluoroborate is 5-8%.
5. a kind of solid chelated acid for water injection well stimulation according to claim 1, it is characterised in that: the work
Property agent be -5 decine -4,7- glycol polyoxyethylene ether of 2,3,7,9- tetramethyl.
6. a kind of solid chelated acid for water injection well stimulation according to claim 1, it is characterised in that: the suppression
Preparation is capper's oil base hydroxyethyl imidazole quinoline.
7. a kind of solid chelated acid for water injection well stimulation according to claim 1, it is characterised in that: the stabilization
Agent is made of arabo-ascorbic acid and nitrilotriacetic acid, and weight percent is the weight of arabo-ascorbic acid in the stabilizer of 5-10%
Percentage is 3-6%, and the weight percent of nitrilotriacetic acid is 2-4%.
8. a kind of solid chelated acid for water injection well stimulation according to claim 1, it is characterised in that: the bonding
Agent is made of stearic acid 1801 and Span-60, and weight percent is the weight hundred of stearic acid 1801 in the adhesive of 15-30%
Divide than being 10-20%, the weight percent of Span-60 is 5-10%.
9. a kind of preparation method of the solid chelated acid for water injection well stimulation, it is characterised in that steps are as follows:
Step 1) stock, the raw material of the solid chelated acid for water injection well stimulation is weighed by formula ratio:
Host agent is 30-40%, adjuvant 20-30%, reinforcing agent 10-15%, activating agent 3-8%, inhibitor 2-3%, stabilizer
It is 15-30% for 5-10% and adhesive；
The adhesive of formula ratio is ground to grinder through 100 mesh by step 2 under conditions of protection of liquid nitrogen, obtains powder, to
With；
Step 3) will mediate built-in temperature and increase and control constant temperature in 40-42 DEG C, and the host agent of formula ratio is added, and stir 20-
30min；The inhibitor of formula ratio is added, the reinforcing agent and adjuvant of formula ratio are added immediately, stirs 30-50min；
Step 4) is cooling by the mixture of step 3), is sieved with 30-50 mesh screen, is not mediated in kneader by the continuation of sieve
To all passing through 30-50 mesh screen；The mixture for crossing sieve is added again in kneader and controls constant temperature in 50-52 DEG C, is added
Enter the activating agent and stabilizer of formula ratio, stirs 20-30min；
The powder of the grinding of step 2 is slowly added into the mixture that step 4) mixes by step 5), stirs 20-30min；
Kneader temperature is closed, continues to stir 20-30min, is sieved with 20-40 mesh screen, does not continue to mediate to all logical by what is sieved
20-40 mesh screen is crossed, that is, is used for the solid chelated acid of water injection well stimulation.
10. a kind of preparation method of solid chelated acid for water injection well stimulation according to claim 9, feature exist
In: the host agent is made of one or two, sulfamic acid, hydroxy ethylene diphosphonic acid in hydrazine hydrochloride and double hydrazine hydrochlorides,
Weight percent is in the host agent of 30-40%: one or two kinds of weight percent is 10-15% in hydrazine hydrochloride and double hydrazine hydrochlorides,
The weight percent of sulfamic acid is 10-12%, and the weight percent of hydroxy ethylene diphosphonic acid is 10-13%；The adjuvant
It being made of urea nitrate and urea phosphate, weight percent is in the adjuvant of 20-30%, and the weight percent of urea nitrate is 15-20%,
The weight percent of urea phosphate is 5-10%；The reinforcing agent is made of ammonium acid fluoride and ammonium fluoroborate, and weight percent is
In the reinforcing agent of 10-15%, the weight percent of ammonium acid fluoride is 5-7%, and the weight percent of ammonium fluoroborate is 5-8%；Described
Activating agent is -5 decine -4,7- glycol polyoxyethylene ether of 2,3,7,9- tetramethyl；The inhibitor is capper's oil base ethoxy
Imidazoline；The stabilizer is made of arabo-ascorbic acid and nitrilotriacetic acid, and weight percent is the stabilizer of 5-10%
In, the weight percent of arabo-ascorbic acid is 3-6%, and the weight percent of nitrilotriacetic acid is 2-4%；The adhesive be by
Stearic acid 1801 and Span-60 composition, weight percent are in the adhesive of 15-30%, and the weight percent of stearic acid 1801 is
The weight percent of 10-20%, Span-60 are 5-10%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114525123A (en) * | 2020-11-23 | 2022-05-24 | 中国石油天然气股份有限公司 | Slow-release acid and preparation and application thereof |
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| WO2016036555A1 (en) * | 2014-09-04 | 2016-03-10 | Ideal Energy Solutions IP Control, LLC | Aqueous cleaning composition and method |
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