WO2025102481A1 - 除垢组合物、除垢剂及制备方法和应用 - Google Patents

除垢组合物、除垢剂及制备方法和应用 Download PDF

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Publication number
WO2025102481A1
WO2025102481A1 PCT/CN2023/140284 CN2023140284W WO2025102481A1 WO 2025102481 A1 WO2025102481 A1 WO 2025102481A1 CN 2023140284 W CN2023140284 W CN 2023140284W WO 2025102481 A1 WO2025102481 A1 WO 2025102481A1
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Prior art keywords
descaling
chelating
agent
parts
descaling composition
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English (en)
French (fr)
Inventor
曹立虎
吴红军
何新兴
潘昭才
刘洪涛
高文祥
黄锟
范磊
孙涛
杨化龙
孙晓飞
刘国华
赵鹏
张宝
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Petrochina Co Ltd
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Petrochina Co Ltd
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Publication of WO2025102481A1 publication Critical patent/WO2025102481A1/zh
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • C02F5/14—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus
    • 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
    • C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
    • 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
    • C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
    • C09K8/524—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning organic depositions, e.g. paraffins or asphaltenes
    • 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
    • C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
    • C09K8/528—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning inorganic depositions, e.g. sulfates or carbonates
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B37/00—Methods or apparatus for cleaning boreholes or wells
    • E21B37/06—Methods or apparatus for cleaning boreholes or wells using chemical means for preventing or limiting, e.g. eliminating, the deposition of paraffins or like substances

Definitions

  • the invention relates to the technical field of oil and gas production engineering, and in particular to a descaling composition, a descaling agent, a preparation method and application thereof.
  • Scale clogging exists in gas fields such as Saudi Arabia's Khuff, Argentina's Consientio, Norway's Vega, and domestic gas fields such as Keshen, Dina, Anyue, Yuanba, Daniudi, and Yulin, which seriously affects the release of gas field production capacity and wellbore integrity.
  • Non-acidic unblocking fluid is based on the principle of chelation descaling. It uses the coordination groups in the chelating agent molecules and the coordination bonds formed with cations such as Ca 2+ and Ba 2+ to "convert" the scale blocks into more stable and water-soluble complexes. Chelation descaling has the two major advantages of extremely low corrosion and a large number of descaling types, and is an ideal substitute for acid.
  • non-acidic unblocking fluids also have shortcomings such as low scale dissolution rate, and most of the non-acidic unblocking fluids currently on the market have a high pH value, which is not conducive to the use of non-acidic unblocking fluids. It may accelerate the scaling of water with high mineralization near the production layer and affect its effect.
  • the purpose of the present invention is to overcome the problem of scale blockage in high-temperature oil and gas wells in the prior art, and to provide a descaling composition, a descaling agent, a preparation method and an application.
  • the descaling agent is a neutral descaling agent, has the characteristics of high temperature resistance, strong scale dissolving performance and low corrosiveness, and can be used for descaling high-temperature oil and gas wells.
  • the first aspect of the present invention provides a descaling composition, which comprises: a polyamino acid chelating agent, a synergist, a chelating catalyst, a chelating stabilizer, a penetrating dispersant, a pH regulator and a solvent; wherein the pH value of the descaling composition is 7 to 8; and the polyamino acid chelating agent has a structure shown in Formula I:
  • R 1 is dialkylamino, alkylamino, amino, hydroxy, alkoxy, amide, acyloxy, carboxymethyl or carboxyl.
  • a second aspect of the present invention provides a method for preparing a descaling agent, the preparation method comprising:
  • the polyamino acid chelating agent, the synergist, the chelating catalyst and the chelating stabilizer are first mixed with water to obtain a first mixture;
  • the pH value of the descaling composition is 7-8;
  • the polyamino acid chelating agent has a structure shown in Formula I:
  • R 1 is dialkylamino, alkylamino, amino, hydroxy, alkoxy, amide, acyloxy, carboxymethyl or carboxyl.
  • the third aspect of the present invention provides a descaling agent prepared by the preparation method described in the second aspect.
  • the fourth aspect of the present invention provides use of the descaling composition described in the first aspect or the descaling agent described in the third aspect in an oil and gas well.
  • the polyamino-polyacid chelating agent used in the descaling composition of the present invention contains multiple amino groups, carboxyl groups, hydroxyl groups and electron-donating groups R 1 , so that it has a strong electron-donating ability, and the carbon chain is extended by grafting modification of the carboxyl group, thereby improving the surface activity of the molecule, making it easier to combine with metal ions to form a stable chelate, and enhancing its temperature resistance;
  • the descaling agent prepared from the descaling composition of the present invention is a neutral descaling agent with low corrosiveness.
  • the descaling agent of the present invention has the characteristics of good scale dissolving effect (the scale dissolving rate of calcium carbonate, calcium sulfate and barium sulfate is relatively large), low corrosion, excellent temperature resistance, wide application range, non-toxic and environmentally friendly, and has good compatibility with formation water, will not cause damage to the formation and pipeline, and can effectively solve the clogging problem of inorganic insoluble scale in high-temperature and high-pressure gas wells.
  • FIG. 1 is an infrared spectrum of the composite solid electrolyte prepared in Preparation Example 1 of the present invention.
  • the first aspect of the present invention provides a descaling composition, which comprises: a polyamino acid chelating agent, a synergist, a chelating catalyst, a chelating stabilizer, a penetrating dispersant, a pH regulator and a solvent; wherein the pH value of the descaling composition is 7 to 8; and the polyamino acid chelating agent has a structure shown in Formula I:
  • R 1 is dialkylamino (-NR 2 ), alkylamino (-NHR), amino (-NH 2 ), hydroxy (-OH), alkoxy (-OR), amide (-NHCOR), acyloxy (-OCOR), carboxymethyl (-CH 2 COOH) or carboxyl (-COOH).
  • R is preferably selected from a C 1 -C 10 straight or branched chain alkyl group.
  • the polyamino polyacid chelating agent contains multiple amino groups, carboxyl groups, hydroxyl groups and electron-donating groups R1 , which makes it have strong electron-donating ability, and through the grafting modification of carboxyl groups, the carbon chain is extended, the surface activity of the molecule is improved, and it is easier to combine with metal ions to form a stable chelate, and its temperature resistance is enhanced.
  • the descaling composition of the present invention realizes efficient descaling of high-temperature (120-180° C.) oil and gas wells through the synergistic effect of various components, and the descaling composition of the present invention is controlled to be neutral so as to have low corrosivity.
  • the synthesis route of the polyaminocarboxylic acid chelating agent is as follows:
  • the present invention provides a method for preparing a polyaminocarboxylic acid chelating agent, which specifically comprises the following steps:
  • step S2 mixing the intermediate 1 obtained in step S1 with acetic anhydride and dry pyridine and reacting the mixture at 60-70° C. for 5-6 hours to obtain intermediate 2;
  • step S3 adding the intermediate 2 obtained in step S2 and ethylene glycol in a molar ratio of 1:2 to 2.1 into a round-bottom flask, adding DMF as a solvent, heating in a water bath to 60 to 70° C., starting stirring, and adding 0.1 to 1.2% of p-toluenesulfonic acid as a catalyst accounting for the total reaction amount, reacting for 5 to 6 hours, to obtain a polyaminocarboxylic acid chelating agent having a structure shown in formula I.
  • the raw material 1 is selected from the structure shown in formula (1):
  • R 1 is dialkylamino (-NR 2 ), alkylamino (-NHR), amino (-NH 2 ), hydroxyl (-OH), alkoxy (-OR), amide (-NHCOR), acyloxy (-OCOR), carboxymethyl (-CH 2 COOH) or carboxyl (-COOH).
  • the descaling composition includes, by weight: 10 to 15 parts of a polyaminocarboxylic acid chelating agent, 1 to 2 parts of a synergist, 0.5 to 1 part of a chelating catalyst, 0.5 to 1 part of a chelating stabilizer, 0.5 to 1 part of a penetrating dispersant, 5 to 10 parts of a pH adjuster and 70 to 82.5 parts of a solvent.
  • the solvent is preferably water.
  • the synergist is a mixture of polyepoxysuccinic acid and polyaspartic acid.
  • the content of polyepoxysuccinic acid is 30-40 wt %, and the content of polyaspartic acid is 60-70 wt %.
  • a mixture of polyepoxysuccinic acid and polyaspartic acid is used as a synergist, which has strong permeability.
  • the synergistic effect between the two it can effectively inhibit the aggregation and nucleation of scale ions, play a role in dispersing scale samples, enhancing the scale removal and unblocking effect, and has a certain corrosion inhibition effect; at the same time, the synergist can be adsorbed on the pipe wall to form a film, further inhibiting the adhesion and deposition of scale samples on the pipe wall.
  • the chelate catalyst is a mixture of ammonium chloride and sodium nitrite.
  • the content of ammonium chloride is 40-50 wt %, and the content of sodium nitrite is 50-60 wt %.
  • the main functions of the chelating catalyst are: on the one hand, it increases the solubility of the sparingly soluble inorganic scale through the ion effect; on the other hand, the sodium nitrite and ammonium chloride react to produce a small amount of nitrogen, which can enter the tiny gaps of the scale sample, increase the permeability of the scale sample, and accelerate the chelation and dissolution rate of the chelating agent and the scale sample to a certain extent.
  • the chelating stabilizer is selected from one or more of sodium citrate, sodium acetate, sodium formate and sodium gluconate, preferably sodium citrate.
  • iron-containing corrosion products will be deposited on the adsorption surface with the metal pipe wall.
  • the main function of the chelating stabilizer is to remove the insoluble iron in the scale, which can improve the peeling effect of the scale on the pipe wall.
  • the osmotic dispersant is a mixture of polyethylene glycol PEG-600 and petroleum sulfonate.
  • the content of polyethylene glycol PEG-600 is 40-50 wt %, and the content of petroleum sulfonate is 50-60 wt %.
  • the main functions of the penetrating dispersant are: on the one hand, it plays a certain dispersing role; on the other hand, it can change the surface properties of the oily scale sample, make the scale sample surface hydrophilic, enhance the penetration of the chelating agent into the interior of the scale sample, and make the scale sample easier to peel off.
  • the pH adjuster is selected from one or more of sodium hydroxide, ammonia water and potassium hydroxide, preferably sodium hydroxide.
  • the descaling composition adopts a pH regulator to adjust the pH value to 7-8.
  • the descaling composition of the present invention has the characteristics of good scale dissolving effect (large scale dissolving rate for calcium carbonate, calcium sulfate and barium sulfate), low corrosion, excellent temperature resistance, wide application range, non-toxic and environmental protection, etc., and has good compatibility with formation water, will not cause damage to the formation and pipeline, and can effectively solve the blockage problem of inorganic insoluble scale in high-temperature and high-pressure gas wells.
  • a second aspect of the present invention provides a method for preparing a descaling agent, the preparation method comprising:
  • the polyamino acid chelating agent, the synergist, the chelating catalyst and the chelating stabilizer are first mixed with water to obtain a first mixture;
  • the pH value of the descaling composition is 7-8;
  • the polyamino acid chelating agent has a structure shown in Formula I:
  • R 1 is dialkylamino (-NR 2 ), alkylamino (-NHR), amino (-NH 2 ), hydroxy (-OH), alkoxy (-OR), amide (-NHCOR), acyloxy (-OCOR), carboxymethyl (-CH 2 COOH) or carboxyl (-COOH).
  • R is preferably selected from a C 1 -C 10 straight or branched chain alkyl group.
  • the polyamino polyacid chelating agent contains multiple amino groups, carboxyl groups, hydroxyl groups and electron-donating groups R1 , which makes it have strong electron-donating ability, and through the grafting modification of carboxyl groups, the carbon chain is extended, the surface activity of the molecule is improved, and it is easier to combine with metal ions to form a stable chelate, and its temperature resistance is enhanced.
  • the descaling agent prepared from the descaling composition adopts a pH adjusting agent to adjust the pH value to 7-8.
  • the neutral descaling agent of the present invention has the characteristics of good scale dissolving effect (large scale dissolving rate for calcium carbonate, calcium sulfate and barium sulfate), low corrosion, excellent temperature resistance, wide application range, non-toxic and environmentally friendly, etc., and has good compatibility with formation water, will not cause damage to the formation and pipeline, and can effectively solve the blockage problem of inorganic insoluble scale in high-temperature and high-pressure gas wells.
  • the descaling composition of the present invention realizes efficient descaling of high-temperature (120-180° C.) oil and gas wells through the synergistic effect of various components.
  • the descaling composition of the present invention is controlled to be neutral so as to have low corrosiveness.
  • polyaminocarboxylic acid chelating agent by weight, there are 10 to 15 parts of polyaminocarboxylic acid chelating agent, 1 to 2 parts of synergist, 0.5 to 1 part of chelating catalyst, 0.5 to 1 part of chelating stabilizer, 0.5 to 1 part of penetrating dispersant, 5 to 10 parts of pH adjuster and 70 to 82.5 parts of solvent.
  • the solvent is preferably water.
  • the selection range of each component is the same as that of the first aspect. Please refer to the previous description for details and will not be repeated here.
  • the first mixing comprises: mixing at 50 to 70° C. under normal pressure stirring conditions for 30 to 60 minutes.
  • the second mixing comprises: mixing at 50-70° C. for 30-60 min, and controlling the pH value at 7-8.
  • the third aspect of the present invention provides a descaling agent prepared by the preparation method described in the second aspect.
  • the fourth aspect of the present invention provides use of the descaling composition described in the first aspect or the descaling agent described in the third aspect in an oil and gas well.
  • the descaling agent of the present invention is a neutral descaling agent (pH is 7-8), which has the characteristics of good scale dissolving effect, low corrosion, excellent temperature resistance, wide application range, non-toxicity and environmental protection, and has good compatibility with formation water, will not cause damage to the formation and pipeline, and can effectively solve the blockage problem of inorganic insoluble scale in high-temperature and high-pressure gas wells.
  • the descaling agent of the present invention has a wide application range and can be used at low temperatures as well as high temperatures.
  • the temperature inside the oil and gas well is 80-180°C, preferably 120-180°C.
  • the preparation method of the polyamino acid chelating agent specifically comprises the following steps:
  • Hydrochloric acid is added to adjust the pH to about 1, and the intermediate 1 is obtained by filtration; then the intermediate 1 is mixed with acetic anhydride and dry pyridine and reacted at 60°C for 5 hours to obtain the intermediate 2; then the intermediate 2 and ethylene glycol are added to a round-bottom flask at a molar ratio of 1:2, DMF is added as a solvent, the system is heated to 60°C in a water bath, stirring is started, and p-toluenesulfonic acid accounting for 0.1% of the total reaction volume is added as a catalyst. After reacting for 5 hours, a product having the structure shown in Formula I-1 is obtained.
  • FIG1 is an infrared spectrum of Formula I-1 obtained in Preparation Example 1.
  • the peak at 3411 cm -1 is caused by the stretching vibration of -OH
  • 1332 cm -1 is caused by the asymmetric stretching vibration of the ester group COC.
  • the preparation method of the polyamino acid chelating agent specifically comprises the following steps:
  • a descaling composition comprises, by weight: 10 parts of a polyamino acid chelating agent prepared in Preparation Example 1; 1 part of a synergist; 0.5 parts of a chelating catalyst; 0.5 parts of sodium citrate; 0.5 parts of a penetrating dispersant; 5 parts of sodium hydroxide, and 82.5 parts of water; wherein the polyamino acid chelating agent has a structure as shown in Formula I-1, the synergist comprises 30 wt% of polyepoxysuccinic acid and 70 wt% of polyaspartic acid (based on the total weight of the synergist); the chelating catalyst comprises 40 wt% of sodium nitrite and 60 wt% of ammonium chloride (based on the total weight of the chelating catalyst); and the penetrating dispersant comprises 40 wt% of polyethylene glycol PEG-600 and 60 wt% of petroleum sulfonate (based on the total weight of the penetrating dispers
  • the preparation of a descaling agent comprises the following steps: adding an appropriate amount of water into a reaction kettle, starting stirring, sequentially adding the above-mentioned formula amounts of a polyamino acid chelating agent, a synergist, a chelating catalyst and a chelating stabilizer sodium citrate, stirring for 50 minutes, adding the above-mentioned formula amount of a pH regulator sodium hydroxide, maintaining the temperature in the kettle at 60°C and the pH value at 7, then adding the above-mentioned formula amount of a penetrating dispersant and continuing stirring for 30 minutes to obtain the descaling agent.
  • a descaling composition comprising, by weight: the polyamino acid chelate prepared in Preparation Example 1 15 parts of mixture; 2 parts of synergist; 1 part of chelate catalyst; 1 part of sodium citrate; 1 part of penetrant; 10 parts of sodium hydroxide, 70 parts of water; wherein, the compositions of the synergist, the chelate catalyst and the penetrating dispersant are respectively the same as those in Example 1.
  • the pH value is controlled at 7.5 to prepare a descaling agent.
  • a descaling composition comprises, by weight: 10 parts of the polyamino acid chelating agent prepared in Preparation Example 1; 2 parts of a synergist; 1 part of a chelating catalyst; 1 part of sodium citrate; 0.5 parts of a penetrating dispersant; 5 parts of sodium hydroxide and 80.5 parts of water; wherein the synergist comprises 40 wt% of polyepoxysuccinic acid and 60 wt% of polyaspartic acid; the chelating catalyst comprises 40 wt% of sodium nitrite and 60 wt% of ammonium chloride; and the penetrating dispersant comprises 40 wt% of polyethylene glycol PEG-600 and 60 wt% of petroleum sulfonate.
  • the pH value was controlled at 7.1 to prepare a descaling agent.
  • a descaling composition comprises, by weight: 10 parts of the polyamino acid chelating agent prepared in Preparation Example 1; 1 part of a synergist; 0.5 parts of a chelating catalyst; 1 part of sodium citrate; 1 part of a penetrating dispersant; 5 parts of sodium hydroxide, and 81.5 parts of water; wherein the synergist comprises 40 wt% of polyepoxysuccinic acid and 60 wt% of polyaspartic acid; the chelating catalyst comprises 50 wt% of sodium nitrite and 50 wt% of ammonium chloride; and the penetrating dispersant comprises 50 wt% of polyethylene glycol PEG-600 and 50 wt% of petroleum sulfonate.
  • the pH value was controlled at 7.1 to prepare a descaling agent.
  • a descaling composition comprises, by weight: 15 parts of the polyamino acid chelating agent prepared in Preparation Example 1; 1 part of a synergist; 0.5 parts of a chelating catalyst; 0.5 parts of sodium citrate; 0.5 parts of a penetrating dispersant; 10 parts of sodium hydroxide, and 72.5 parts of water; wherein the compositions of the synergist, the chelating catalyst and the penetrating dispersant are respectively the same as those in Example 1.
  • the pH value was controlled at 7.8 to prepare a descaling agent.
  • a descaling composition comprises, by weight: 15 parts of the polyamino acid chelating agent prepared in Preparation Example 1; 2 parts of a synergist; 0.5 parts of a chelating catalyst; 0.5 parts of sodium citrate; 1 part of a penetrating dispersant; 10 parts of sodium hydroxide, and 71 parts of water; wherein the compositions of the synergist, the chelating catalyst and the penetrating dispersant are respectively the same as those in Example 1.
  • the pH value is controlled at 8 to prepare a descaling agent.
  • a descaling composition comprising, by weight: 13 parts of the polyamino acid chelating agent prepared in Preparation Example 1; 1.5 parts of a synergist; 0.8 parts of a chelating catalyst; 0.8 parts of sodium citrate; 0.8 parts of a penetrating dispersant; 8 parts of sodium hydroxide, and 75.1 parts of water; wherein the compositions of the synergist, the chelating catalyst and the penetrating dispersant are respectively the same as those in Example 1.
  • the pH value was controlled at 7.6 to prepare a descaling agent.
  • Example 1 The formulation and method of Example 1 are the same as those of Example 1, except that the synergist comprises 35 wt % of polyepoxysuccinic acid and 65 wt % of polyaspartic acid, and the remaining components are the same as those of Example 1.
  • the pH value is controlled at 7 to prepare a descaling agent.
  • the pH value is controlled at 7 to prepare a descaling agent.
  • Example 1 The formulation and method of Example 1 are the same as those of Example 1, except that the synergist is polyaspartic acid (100 wt %, based on the total weight of the synergist), and the remaining components are the same as those of Example 1.
  • the pH value is controlled at 7 to prepare a descaling agent.
  • Example 1 The formulation and method of Example 1 are the same as those of Example 1, except that the penetrating dispersant includes 50 wt % of polyethylene glycol PEG-600 and 50 wt % of petroleum sulfonate, and the remaining components are the same as those of Example 1.
  • the penetrating dispersant includes 50 wt % of polyethylene glycol PEG-600 and 50 wt % of petroleum sulfonate, and the remaining components are the same as those of Example 1.
  • the pH value is controlled at 7 to prepare a descaling agent.
  • the chelate catalyst includes 50wt% sodium nitrite and 50wt% ammonium chloride, and the other components are the same as those of Example 1.
  • the chelate catalyst includes 35wt% sodium nitrite and 65wt% ammonium chloride, and the other components are the same as those of Example 1.
  • the pH value is controlled at 7 to prepare a descaling agent.
  • Example 1 The formulation and method of Example 1 are the same as those of Example 1, except that the synergist comprises 40 wt % of polyepoxysuccinic acid and 60 wt % of polyaspartic acid, and the remaining components are the same as those of Example 1.
  • the pH value is controlled at 7 to prepare a descaling agent.
  • Example 1 uses the polyamino polyacid chelating agent prepared in Preparation Example 2, and the polyamino polyacid chelating agent has the structure shown in Formula I-2, and the other components are the same as Example 1.
  • the pH value is controlled at 7 to prepare a descaling agent.
  • a descaling composition comprising, by weight: the polyamino acid chelating agent prepared in Preparation Example 2, 15 parts of the polyamino acid chelating agent; 1.5 parts of a synergist; 0.8 parts of a chelating catalyst; 0.8 parts of sodium citrate; 0.8 parts of a penetrating dispersant; 8 parts of sodium hydroxide, and 73.1 parts of water; wherein the polyamino acid chelating agent
  • the mixture has the structure shown in Formula I-2, and the compositions of the synergist, the chelating catalyst and the penetrating dispersant are the same as those in Example 1.
  • the pH value was controlled at 7.3 to prepare a descaling agent.
  • Example 1 According to the formula and method of Example 1, the only difference is that the weight portion of sodium hydroxide is 15 parts, and the other components are the same as those in Example 1.
  • a descaling agent was prepared according to the formula of the above descaling composition, and the pH value was controlled at 12, which was an alkaline descaling agent.
  • Example 1 According to the formula and method of Example 1, the only difference is that the weight portion of sodium hydroxide is 1 part, and the other components are the same as those in Example 1.
  • a descaling agent was prepared according to the formula of the above descaling composition, and the pH value was controlled at 3, which was an acidic descaling agent.
  • Example 1 According to the formula and method of Example 1, the only difference is that the chelating agent is diethylenetriaminepentaacetic acid, and the other components are the same as those of Example 1.
  • the pH value is controlled at 7 to prepare a descaling agent.
  • Example 1 The formula and method of Example 1 are the same as those of Example 1, except that the polyamino acid chelating agent is not added. The other components are the same as those of Example 1.
  • the pH value is controlled at 7 to prepare a descaling agent.
  • Example 1 The formula and method of Example 1 are the same as those of Example 1, except that no chelating stabilizer is added.
  • the other components are the same as those of Example 1.
  • the pH value is controlled at 7 to prepare a descaling agent.
  • Example 1 The formula and method of Example 1 are the same as those of Example 1, except that no penetrating dispersant is added. The remaining components are the same as those of Example 1.
  • the pH value is controlled at 7 to prepare a descaling agent.
  • the dissolution rate and corrosion rate are determined as follows:
  • m 0 mass of the scale sample before the scale sample reaction, g;
  • m 1 The mass of the scale sample after the scale sample reacts, g.
  • the descaling agents used in the embodiments of the present invention are all strong penetrating neutral descaling agents, and the scale dissolution rates of calcium carbonate, calcium sulfate and barium sulfate at 120 and 180° C. are higher than those of the control examples. At the same time, they all have faster corrosion rates and can be used in high-temperature oil and gas wells.
  • the neutral descaling agent of the present invention is suitable for descaling and unblocking of high-temperature gas wellbore.
  • the test result of the descaling rate shows that the use temperature thereof can reach 120-180°C.
  • the neutral descaling agent of the present invention has the characteristics of good descaling effect (calcium carbonate descaling rate, calcium sulfate descaling rate and barium sulfate descaling rate are all greater than 70%), low corrosiveness (corrosion rate is less than 0.2g/( m2 ⁇ h)), excellent temperature resistance (80-180°C), wide application range, non-toxic and environmentally friendly, etc., and has good compatibility with formation water, will not cause damage to the formation and pipeline, and can effectively solve the inorganic difficulty of high temperature and high pressure gas wells. Blockage problem caused by scale dissolution.

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Abstract

一种除垢组合物，其包括：多氨基多酸螯合剂、增效剂、螯合催化剂、螯合稳定剂、渗透分散剂、pH调节剂和溶剂；其中，所述除垢组合物的pH值为7～8；所述多氨基多酸螯合剂具有式I所示结构：式I中，R 1为二烷基氨基、烷基氨基、氨基、羟基、烷氧基、酰胺基、酰氧基、羧基甲基或羧基。该除垢组合物采用的多氨基多酸螯合剂中含有多个氨基、羧基、羟基以及给电子基团R 1，使其更容易与金属离子结合形成稳定的螯合物，并增强其耐温性能；且由其制得的中性除垢剂，具有溶垢效果好、腐蚀性低和耐温性能优异等特点，能够有效解决高温高压气井的无机难溶垢的堵塞问题。

Description

除垢组合物、除垢剂及制备方法和应用
相关申请的交叉引用
本申请要求2023年11月13日提交的中国专利申请202311508728.0的权益，该申请的内容通过引用被合并于本文。
技术领域
本发明涉及采油气工程技术领域，具体涉及除垢组合物、除垢剂及制备方法和应用。
背景技术
气井无机垢堵塞是普遍问题，国外沙特Khuff、阿根廷Centenario、挪威Vega等气田以及国内克深、迪那、安岳、元坝、大牛地、榆林等气田均存在垢堵情况，严重影响气田产能释放和井筒完整性。据统计，2017年以来克深、迪那气田56％的气井发生垢堵，影响产能超4000万方/天；安岳气田高磨台缘带48％的气井存在垢堵，影响产能448万方/天；元坝气田发生8口井/18井次垢堵问题，占比22％，其中1口井完全堵死；大牛地气田42％的气井管柱结垢。同时，储层温度越高，地层水中结垢离子浓度越大，结垢趋势越大，超深气井一般地层温度和结垢离子浓度均较高，国内塔里木盆地克深、迪那，四川盆地元坝、普光等超深气田结垢问题相对更为严重。
相比连续油管疏通、水射流等物理解堵技术，化学除垢解堵具有作业时间短、解除近井储层堵塞等优点，已成为气井除垢解堵最常用的手段，其中解堵液体系是技术的关键。传统多利用酸液除垢解堵，具有溶垢率高的优点，但是对于硫酸钙、硫酸钡、硫酸锶等垢，其溶解性较差，同时酸液容易对金属管线产生腐蚀，影响油气田生产管线的安全正常运行以及油气井的正常作业。非酸性解堵液基于螯合除垢原理，利用螯合剂分子中配位基团和与垢物Ca2+、Ba2+等阳离子形成配位键，将垢块“转化”为更稳定、易溶于水的配合物。螯合除垢具有极低腐蚀和除垢类型多两大优点，是酸液的理想替代品。但非酸性解堵液也存在溶垢率低等不足，并且目前市售的多数非酸性解堵液均具有较高的pH值，在使用过程中 可能会加快产层附近高矿化度下水质的结垢，影响其作用效果。
发明内容
本发明的目的是为了克服现有技术存在的高温油气井垢堵的问题，提供除垢组合物、除垢剂及制备方法和应用，该除垢剂为中性除垢剂，具有耐高温、溶垢性能强和腐蚀性低的特点，可用于高温油气井除垢。
为了实现上述目的，本发明第一方面提供一种除垢组合物，所述除垢组合物包括：多氨基多酸螯合剂、增效剂、螯合催化剂、螯合稳定剂、渗透分散剂、pH调节剂和溶剂；其中，所述除垢组合物的pH值为7～8；所述多氨基多酸螯合剂具有式I所示结构：
式I中，R1为二烷基氨基、烷基氨基、氨基、羟基、烷氧基、酰胺基、酰氧基、羧基甲基或羧基。
本发明第二方面提供一种除垢剂的制备方法，所述制备方法包括：
在搅拌条件下，将多氨基多酸螯合剂、增效剂、螯合催化剂和螯合稳定剂与水进行第一混合，得到第一混合物；
在所述第一混合物中加入pH调节剂，在50～70℃下将pH值控制在7～8，然后加入渗透分散剂，进行第二混合，得到中性除垢剂；
其中，所述除垢组合物的pH值为7～8；所述多氨基多酸螯合剂具有式I所示结构：
式I中，R1为二烷基氨基、烷基氨基、氨基、羟基、烷氧基、酰胺基、酰氧基、羧基甲基或羧基。
本发明第三方面提供由前述第二方面所述的制备方法制得的除垢剂。
本发明第四方面提供前述第一方面所述的除垢组合物或前述第三方面所述的除垢剂在油气井中的应用。
通过上述技术方案，本发明所取得的有益技术效果如下：
1)本发明除垢组合物采用的多氨基多酸螯合剂中含有多个氨基、羧基、羟基以及给电子基团R1，使其具备较强的给电子能力，并通过对羧基的接枝改性来延长碳链，改善分子的表面活性，使其更容易与金属离子结合形成稳定的螯合物，并增强其耐温性能；由本发明除垢组合物制得的除垢剂为中性除垢剂，具有低腐蚀性。
2)本发明的除垢剂具有溶垢效果好(对碳酸钙、硫酸钙和硫酸钡的溶垢率都较大)、腐蚀性低、耐温性能优异、适用范围广、无毒环保等特点，并与地层水具有很好的配伍性，不会对地层及管道造成伤害，能够有效解决高温高压气井的无机难溶垢的堵塞问题。
附图说明
图1是本发明制备例1制得的复合固态电解质的红外光谱图。
具体实施方式
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以 彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。
本发明第一方面提供一种除垢组合物，所述除垢组合物包括：多氨基多酸螯合剂、增效剂、螯合催化剂、螯合稳定剂、渗透分散剂、pH调节剂和溶剂；其中，所述除垢组合物的pH值为7～8；所述多氨基多酸螯合剂具有式I所示结构：
式I中，R1为二烷基氨基(-NR2)、烷基氨基(-NHR)、氨基(-NH2)、羟基(-OH)、烷氧基(-OR)、酰胺基(-NHCOR)、酰氧基(-OCOR)、羧基甲基(-CH2COOH)或羧基(-COOH)。
在本发明中，R优选选自C1-C10的直链或支链烷基。
在本发明中，多氨基多酸螯合剂中含有多个氨基、羧基、羟基以及给电子基团R1，使其具备较强的给电子能力，并通过对羧基的接枝改性来延长碳链，改善分子的表面活性，使其更容易与金属离子结合形成稳定的螯合物，并增强其耐温性能。
本发明的除垢组合物通过各组分之间的协同作用，实现高温(120～180℃)油气井的高效除垢，且控制本发明的除垢组合物为中性，使其具有低腐蚀性。
在本发明的一些实施方式中，多氨基羧酸螯合剂的合成路线如下：

本发明提供了一种多氨基羧酸螯合剂的制备方法，具体包括如下步骤：
S1、中间体1的制备：
S11、将原料1与30％氢氧化钠水溶液按照质量比1:0.9～1.1加入到三口烧瓶中；
S12、用去离子水配制质量浓度为50％的氯乙酸水溶液(氯乙酸与原料1物质的量比为1：0.9～1.1)，装入恒压滴液漏斗中备用；
S13、将氢氧化钠水溶液装入另一恒压滴液漏斗中备用，升高反应温度值80～90℃，同时滴加S11和S12中得到的溶液，保持体系温度在80～90℃，保持pH在10～11，滴加完毕抽真空抽出水继续反应2h，加盐酸调pH至1左右，过滤得到中间体1；
S2、将步骤S1得到的中间体1与乙酐、干燥的吡啶混合后在60～70℃下反应5～6h得到中间体2；
S3、将步骤S2得到的中间体2与乙二醇按照物质的量比为1:2～2.1加入到圆底烧瓶中，加入DMF作为溶剂，水浴加热至60～70℃，开启搅拌，并加入占反应总量为0.1～1.2％的对甲苯磺酸作为催化剂，反应5～6h后，得到具有式I所示结构的多氨基羧酸螯合剂。
本发明中，原料1选自具有式(1)所示结构：
式(1)中，R1为二烷基氨基(-NR2)、烷基氨基(-NHR)、氨基(-NH2)、羟基(-OH)、烷氧基(-OR)、酰胺基(-NHCOR)、酰氧基(-OCOR)、羧基甲基(-CH2COOH)或羧基(-COOH)。
在本发明的一些实施方式中，按重量份计，所述除垢组合物包括：多氨基羧酸螯合剂10～15份，增效剂1～2份，螯合催化剂0.5～1份，螯合稳定剂0.5～1份，渗透分散剂0.5～1份，pH调节剂5～10份和溶剂70～82.5份。
本发明中，溶剂优选为水。
在本发明的一些实施方式中，所述增效剂为聚环氧琥珀酸和聚天门冬氨酸的混合物。
在本发明的一些实施方式中，以所述增效剂的总重量计，聚环氧琥珀酸的含量为30～40wt％，聚天门冬氨酸的含量为60～70wt％。
在本发明中，采用聚环氧琥珀酸和聚天门冬氨酸的混合物作为增效剂，具有强渗透性，通过两者之间的协同作用，能够有效抑制成垢离子聚集成核，起到分散垢样、增强除垢的解堵效果的作用，并具有一定的缓蚀效果；同时该增效剂能够在管壁吸附成膜，进一步抑制了垢样在管壁的附着沉积。
在本发明的一些实施方式中，所述螯合催化剂为氯化铵和亚硝酸钠的混合物。
在本发明的一些实施方式中，以所述螯合催化剂的总重量计，氯化铵的含量为40-50wt％，亚硝酸钠的含量为50～60wt％。
在本发明中，螯合催化剂的主要作用：一方面是通过离子效应提高难溶无机垢的溶解度；另一方面，亚硝酸钠和氯化铵反应产生少量氮气，能够进入到垢样细小空隙，提高垢样的渗透率，能从一定程度上加快螯合剂与垢样的螯合溶解速度。
在本发明的一些实施方式中，所述螯合稳定剂选自柠檬酸钠、乙酸钠、甲酸钠和葡萄糖酸钠中的一种或多种，优选为柠檬酸钠。
在本发明中，针对于已经附着在管壁表面的垢样，在与金属管壁的吸附面会产生含铁的腐蚀产物沉积，螯合稳定剂的主要作用是用来清除垢质中铁的不溶物，能够提高垢样在管壁的剥落效果。
在本发明的一些实施方式中，所述渗透分散剂选自聚乙二醇PEG-600、脂肪醇聚氧乙烯醚硫酸钠、脂肪醇聚氧乙烯醚和石油磺酸盐中的一种或多种。
在本发明的一些实施方式中，所述渗透分散剂为聚乙二醇PEG-600和石油磺酸盐的混合物。
在本发明的一些实施方式中，以所述渗透分散剂的总重量计，聚乙二醇PEG-600的含量为40～50wt％，石油磺酸盐的含量为50～60wt％。
在本发明中，渗透分散剂的主要作用：一方面是起到一定的分散作用；另一方面，能够改变含油垢样表面性质，使垢样表面具备亲水性，增强螯合剂向垢样内部的渗透作用，使垢样更易剥落。
在本发明的一些实施方式中，所述pH调节剂选自氢氧化钠、氨水和氢氧化钾中的一种或多种，优选为氢氧化钠。
在本发明中，除垢组合物采用pH调节剂将pH值调至7～8，相比于酸性和碱性除垢，本发明的除垢组合物具有溶垢效果好(对碳酸钙、硫酸钙和硫酸钡的溶垢率都较大)、腐蚀性低、耐温性能优异、适用范围广、无毒环保等特点，并与地层水具有很好的配伍性，不会对地层及管道造成伤害，能够有效解决高温高压气井的无机难溶垢的堵塞问题。
本发明第二方面提供一种除垢剂的制备方法，所述制备方法包括：
在搅拌条件下，将多氨基多酸螯合剂、增效剂、螯合催化剂和螯合稳定剂与水进行第一混合，得到第一混合物；
在所述第一混合物中加入pH调节剂和渗透分散剂，进行第二混合，得到除垢剂；
其中，所述除垢组合物的pH值为7～8；所述多氨基多酸螯合剂具有式I所示结构：
式I中，R1为二烷基氨基(-NR2)、烷基氨基(-NHR)、氨基(-NH2)、羟基(-OH)、烷氧基(-OR)、酰胺基(-NHCOR)、酰氧基(-OCOR)、羧基甲基(-CH2COOH)或羧基(-COOH)。
在本发明中，R优选选自C1-C10的直链或支链烷基。
在本发明中，多氨基多酸螯合剂中含有多个氨基、羧基、羟基以及给电子基团R1，使其具备较强的给电子能力，并通过对羧基的接枝改性来延长碳链，改善分子的表面活性，使其更容易与金属离子结合形成稳定的螯合物，并增强其耐温性能。
在本发明中，由除垢组合物制得的除垢剂，采用pH调节剂将pH值调至7～8，相比于酸性和碱性除垢，本发明的中性除垢剂具有溶垢效果好(对碳酸钙、硫酸钙和硫酸钡的溶垢率都较大)、腐蚀性低、耐温性能优异、适用范围广、无毒环保等特点，并与地层水具有很好的配伍性，不会对地层及管道造成伤害，能够有效解决高温高压气井的无机难溶垢的堵塞问题。
本发明的除垢组合物通过各组分之间的协同作用，实现高温(120～180℃)油气井的高效除垢。且控制本发明的除垢组合物为中性，使其具有低腐蚀性。
在本发明的一些实施方式中，按重量份计，多氨基羧酸螯合剂10～15份，增效剂1～2份，螯合催化剂0.5～1份，螯合稳定剂0.5～1份，渗透分散剂0.5～1份，pH调节剂5～10份和溶剂70～82.5份。
本发明中，溶剂优选为水。
本发明中，各组分的选择范围与前述第一方面相同，具体请参见前面的描述，在此不再赘述。
在本发明的一些实施方式中，所述第一混合包括：在50～70℃的常压搅拌条件下混合30～60min。
在本发明的一些实施方式中，所述第二混合包括：在50～70℃下混合30～60min，并将pH值控制在7～8。
本发明第三方面提供由前述第二方面所述的制备方法制得的除垢剂。
本发明第四方面提供前述第一方面所述的除垢组合物或前述第三方面所述的除垢剂在油气井中的应用。
本发明的除垢剂为中性除垢剂(pH为7～8)，具有溶垢效果好、腐蚀性低、耐温性能优异、适用范围广、无毒环保等特点，并与地层水具有很好的配伍性，不会对地层及管道造成伤害，能够有效解决高温高压气井的无机难溶垢的堵塞问题。
本发明的除垢剂的适用范围广，既可以在低温下使用，也可以在高温下使用。
在本发明的一些实施方式中，所述油气井的井内温度为80～180℃，优选为120～180℃。
以下将通过实施例对本发明进行详细描述。
以下实施例和对比例中，在没有特别说明的情况下，使用的各种原料均来自商购。
制备例1
多氨基多酸螯合剂的制备方法，具体包括如下步骤：
(1)将2,3-二氨基丙酸与30％氢氧化钠水溶液按质量比1:1加入到三口烧瓶中；
(2)用去离子水配制质量浓度为50％的氯乙酸水溶液(氯乙酸与原料1物质的量比为1:1)，装入恒压滴液漏斗中备用；
(3)将氢氧化钠水溶液装入另一恒压滴液漏斗中备用，升高反应温度至80℃，同时滴加(1)和(2)中的溶液，保持体系温度在80℃，保持pH在10～11，滴加完毕抽真空出入水继续反应2h，加盐酸调pH至1左右，过滤得到中间体1；然后将中间体1与乙酐、干燥的吡啶混合后在60℃下反应5h得到中间体2；再将中间体2与乙二醇按照物质的量比为1:2加入到圆底烧瓶中，加入DMF作为溶剂，水浴加热至60℃，开启搅拌，并加入占反应总量为0.1％的对甲苯磺酸作为催化剂，反应5h后，得到具有式I-1所示结构的产物。
具体的合成反应如下：
图1为该制备例1制得的式I-1的红外光谱图。由图1可知，3411cm-1处的峰值是由-OH的伸缩振动引起的，1739cm-1为酯基的C＝O伸缩振动峰，在1587cm-1和1409cm-1为羧基的C＝O伸缩振动引起，1332cm-1是由酯基C-O-C不对称伸缩振动振动引起的，这些结果表明成功合成了具有式I-1所示结构的目标产物。
制备例2
多氨基多酸螯合剂的制备方法，具体包括如下步骤：
(1)将3,4-二氨基丁酸与30％氢氧化钠水溶液按质量比1:1加入到三口烧瓶中；
(2)用去离子水配制质量浓度为50％的氯乙酸水溶液(氯乙酸与原料1物质的量比为1:1)，装入恒压滴液漏斗中备用；
(3)将氢氧化钠水溶液装入另一恒压滴液漏斗中备用，升高反应温度至85℃，同时滴加(1)和(2)中的溶液，保持体系温度在85℃，保持pH在10～11，滴加完毕抽真空出入水继续反应2h，加盐酸调pH至1左右，过滤得到中间体1；然后将中间体1与乙酐、干燥的吡啶混合后在65℃下反应6h得到中间体2；再将中间体2与乙二醇按照物质的量比为1:2加入到圆底烧瓶中，加入DMF作为溶剂，水浴加热至65℃，开启搅拌，并加入占反应总量为0.1％的对甲苯磺酸作为催化剂，反应6h后，得到具有式I-2所示结构的产物。
实施例1
一种除垢组合物，按照重量份数计，包括：制备例1制得的多氨基多酸螯合剂10份；增效剂1份；螯合催化剂0.5份；柠檬酸钠0.5份；渗透分散剂0.5份；氢氧化钠5份，水82.5份；其中，该多氨基多酸螯合剂具有式I-1所示结构，增效剂包括30wt％的聚环氧琥珀酸和70wt％的聚天门冬氨酸(以增效剂的总重量计)；螯合催化剂包括40wt％的亚硝酸钠和60wt％的氯化铵(以螯合催化剂的总重量计)；渗透分散剂包括40wt％的聚乙二醇PEG-600和60wt％的石油磺酸盐(以渗透分散剂的总重量计)。
一种除垢剂的制备包括以下步骤：在反应釜中加入适量的水，开启搅拌，依次加入上述配方量的多氨基多酸螯合剂、增效剂、螯合催化剂和螯合稳定剂柠檬酸钠，搅拌50min后，加入上述配方量的pH调节剂氢氧化钠，保持釜内温度在60℃，pH值控制在7，然后加入上述配方量的渗透分散剂继续搅拌30min，得到除垢剂。
实施例2
一种除垢组合物，按照重量份数计，包括：制备例1制得的多氨基多酸螯 合剂15份；增效剂2份；螯合催化剂1份；柠檬酸钠1份；渗透剂1份；氢氧化钠10份，水70份；其中，其中，增效剂、螯合催化剂和渗透分散剂的组成分别与实施例1对应相同。
按照实施例1的方法，并按照上述除垢组合物的配方，pH值控制在7.5，制备除垢剂。
实施例3
一种除垢组合物，按照重量份数计，包括：制备例1制得的多氨基多酸螯合剂10份；增效剂2份；螯合催化剂1份；柠檬酸钠1份；渗透分散剂0.5份；氢氧化钠5份，水80.5份；其中，增效剂包括40wt％的聚环氧琥珀酸和60wt％的聚天门冬氨酸；螯合催化剂包括40wt％的亚硝酸钠和60wt％的氯化铵；渗透分散剂包括40wt％的聚乙二醇PEG-600和60wt％的石油磺酸盐。
按照实施例1的方法，并按照上述除垢组合物的配方，pH值控制在7.1，制备除垢剂。
实施例4
一种除垢组合物，按照重量份数计，包括：制备例1制得的多氨基多酸螯合剂10份；增效剂1份；螯合催化剂0.5份；柠檬酸钠1份；渗透分散剂1份；氢氧化钠5份，水81.5份；其中，增效剂包括40wt％的聚环氧琥珀酸和60wt％的聚天门冬氨酸；螯合催化剂包括50wt％的亚硝酸钠和50wt％的氯化铵；渗透分散剂包括50wt％的聚乙二醇PEG-600和50wt％的石油磺酸盐。
按照实施例1的方法，并按照上述除垢组合物的配方，pH值控制在7.1，制备除垢剂。
实施例5
一种除垢组合物，按照重量份数计，包括：制备例1制得的多氨基多酸螯合剂15份；增效剂1份；螯合催化剂0.5份；柠檬酸钠0.5份；渗透分散剂0.5份；氢氧化钠10份，水72.5份；其中，增效剂、螯合催化剂和渗透分散剂的组成分别与实施例1对应相同。
按照实施例1的方法，并按照上述除垢组合物的配方，pH值控制在7.8，制备除垢剂。
实施例6
一种除垢组合物，按照重量份数计，包括：制备例1制得的多氨基多酸螯合剂15份；增效剂2份；螯合催化剂0.5份；柠檬酸钠0.5份；渗透分散剂1份；氢氧化钠10份，水71份；其中，增效剂、螯合催化剂和渗透分散剂的组成分别与实施例1对应相同。
按照实施例1的方法，并按照上述除垢组合物的配方，pH值控制在8，制备除垢剂。
实施例7
一种除垢组合物，按照重量份数计，包括：制备例1制得的多氨基多酸螯合剂13份；增效剂1.5份；螯合催化剂0.8份；柠檬酸钠0.8份；渗透分散剂0.8份；氢氧化钠8份，水75.1份；其中，其中，增效剂、螯合催化剂和渗透分散剂的组成分别与实施例1对应相同。
按照实施例1的方法，并按照上述除垢组合物的配方，pH值控制在7.6，制备除垢剂。
实施例8
按照实施例1的配方及方法，不同之处仅在于，增效剂包括35wt％的聚环氧琥珀酸和65wt％的聚天门冬氨酸，其余组分与实施例1相同。
按照实施例1的方法，并按照上述除垢组合物的配方，pH值控制在7，制备除垢剂。
实施例9
按照实施例1的配方及方法，不同之处仅在于，增效剂为聚环氧琥珀酸(100wt％，以增效剂的总重量计)，其余组分与实施例1相同。
按照实施例1的方法，并按照上述除垢组合物的配方，pH值控制在7，制备除垢剂。
实施例10
按照实施例1的配方及方法，不同之处仅在于，增效剂为聚天门冬氨酸(100wt％，以增效剂的总重量计)，其余组分与实施例1相同。
按照实施例1的方法，并按照上述除垢组合物的配方，pH值控制在7，制备除垢剂。
实施例11
按照实施例1的配方及方法，不同之处仅在于，渗透分散剂包括50wt％的聚乙二醇PEG-600和50wt％的石油磺酸盐，其余组分与实施例1相同。
按照实施例1的方法，并按照上述除垢组合物的配方，pH值控制在7，制备除垢剂。
实施例12
按照实施例1的配方及方法，不同之处仅在于，螯合催化剂包括50wt％的亚硝酸钠和50wt％的氯化铵，其余组分与实施例1相同。
按照实施例1的方法，并按照上述除垢组合物的配方，pH值控制在7，制备除垢剂。
实施例13
按照实施例1的配方及方法，不同之处仅在于，螯合催化剂包括35wt％的亚硝酸钠和65wt％的氯化铵，其余组分与实施例1相同。
按照实施例1的方法，并按照上述除垢组合物的配方，pH值控制在7，制备除垢剂。
实施例14
按照实施例1的配方及方法，不同之处仅在于，增效剂包括40wt％的聚环氧琥珀酸和60wt％的聚天门冬氨酸，其余组分与实施例1相同。
按照实施例1的方法，并按照上述除垢组合物的配方，pH值控制在7，制备除垢剂。
实施例15
按照实施例1的配方及方法，不同之处仅在于，本实施例采用制备例2制得的多氨基多酸螯合剂，该多氨基多酸螯合剂具有式I-2所示结构，其余组分与实施例1相同。
按照实施例1的方法，并按照上述除垢组合物的配方，pH值控制在7，制备除垢剂。
实施例16
一种除垢组合物，按照重量份数计，包括：制备例2制得的多氨基多酸螯合剂，多氨基多酸螯合剂15份；增效剂1.5份；螯合催化剂0.8份；柠檬酸钠0.8份；渗透分散剂0.8份；氢氧化钠8份，水73.1份；其中，该多氨基多酸螯 合剂具有式I-2所示结构，增效剂、螯合催化剂和渗透分散剂的组成分别与实施例1对应相同。
按照实施例1的方法，并按照上述除垢组合物的配方，pH值控制在7.3，制备除垢剂。
对比例1
按照实施例1的配方及方法，不同之处仅在于，氢氧化钠的重量份为15份，其余组分与实施例1相同。
按照实施例1的方法，并按照上述除垢组合物的配方制备除垢剂，pH值控制在12，为碱性除垢剂。
对比例2
按照实施例1的配方及方法，不同之处仅在于，氢氧化钠的重量份为1份，其余组分与实施例1相同。
按照实施例1的方法，并按照上述除垢组合物的配方制备除垢剂，pH值控制在3，为酸性除垢剂。
对比例3
按照实施例1的配方及方法，不同之处仅在于，螯合剂为二乙烯三胺五乙酸，其余组分与实施例1相同。
按照实施例1的方法，并按照上述除垢组合物的配方，pH值控制在7，制备除垢剂。
对比例4
按照实施例1的配方及方法，不同之处仅在于，不添加多氨基多酸螯合剂，其余组分与实施例1相同。
按照实施例1的方法，并按照上述除垢组合物的配方，pH值控制在7，制备除垢剂。
对比例5
按照实施例1的配方及方法，不同之处仅在于，不添加增效剂，其余组分与实施例1相同。
按照实施例1的方法，并按照上述除垢组合物的配方，pH值控制在7，制备除垢剂。
对比例6
按照实施例1的配方及方法，不同之处仅在于，不添加螯合稳定剂，其余组分与实施例1相同。
按照实施例1的方法，并按照上述除垢组合物的配方，pH值控制在7，制备除垢剂。
对比例7
按照实施例1的配方及方法，不同之处仅在于，不添加增效剂和螯合稳定剂，其余组分与实施例1相同。
按照实施例1的方法，并按照上述除垢组合物的配方，pH值控制在7，制备除垢剂。
对比例8
按照实施例1的配方及方法，不同之处仅在于，不添加渗透分散剂，其余组分与实施例1相同。
按照实施例1的方法，并按照上述除垢组合物的配方，pH值控制在7，制备除垢剂。
测试例
溶蚀率和腐蚀速率的测定方法如下：
(1)溶蚀率的测定：称取1g垢样，分别加入到50mL的上述实施例1-18和对比例1-7制得的除垢剂中，在120℃和180℃下反应6h后，过滤烘干，通过测定反应前后垢样的质量差计算溶蚀率。
式中：
m0——垢样反应前垢样的质量，g；
m1——垢样反应后垢样的质量，g。
(2)腐蚀速率的测定：将油管用钢(超级13Cr)打磨光亮后经石油醚和乙醇清洗干燥，称重，置于高压釜中。分别通入2L上述实施例1-14和对比例1-7制得的除垢剂，搅拌并升温至180℃，再通入高纯N2维持N2压力为10MPa，在该条件下稳定6h后取出试样，去除试样表面腐蚀产物膜，干燥后称重并计算 腐蚀速率。
表1
通过表1的结果可以看出，采用本发明实施例的除垢剂均为强渗透中性除垢剂，在120和180℃下对碳酸钙、硫酸钙和硫酸钡的溶垢率均高于对比例，同时均有较快的腐蚀速率，均可用于高温油气井。
本发明中性除垢剂适用于高温气井井筒的除垢解堵，通过溶垢率测试结果表明，其使用温度可达到120～180℃。
综上所述，本发明的中性除垢剂具有溶垢效果好(碳酸钙溶垢率、硫酸钙溶垢率和硫酸钡溶垢率均大于70％以上)、腐蚀性低(腐蚀速率小于0.2g/(m2·h))、耐温性能优异(80～180℃)、适用范围广、无毒环保等特点，并与地层水具有很好的配伍性，不会对地层及管道造成伤害，能够有效解决高温高压气井的无机难 溶垢的堵塞问题。
以上详细描述了本发明的优选实施方式，但是，本发明并不限于此。在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，包括各个技术特征以任何其它的合适方式进行组合，这些简单变型和组合同样应当视为本发明所公开的内容，均属于本发明的保护范围。

Claims (15)

  1. 一种除垢组合物，其特征在于，所述除垢组合物包括：多氨基多酸螯合剂、增效剂、螯合催化剂、螯合稳定剂、渗透分散剂、pH调节剂和溶剂；其中，所述除垢组合物的pH值为7～8；所述多氨基多酸螯合剂具有式I所示结构：
    式I中，R1为二烷基氨基、烷基氨基、氨基、羟基、烷氧基、酰胺基、酰氧基、羧基甲基或羧基。
  2. 根据权利要求1所述的除垢组合物，其中，按重量份计，所述除垢组合物包括：多氨基羧酸螯合剂10～15份，增效剂1～2份，螯合催化剂0.5～1份，螯合稳定剂0.5～1份，渗透分散剂0.5～1份，pH调节剂5～10份和溶剂70～82.5份。
  3. 根据权利要求1所述的除垢组合物，其中，所述增效剂为聚环氧琥珀酸和聚天门冬氨酸的混合物。
  4. 根据权利要求3所述的除垢组合物，其中，以所述增效剂的总重量计，聚环氧琥珀酸的含量为30～40wt％，聚天门冬氨酸的含量为60～70wt％。
  5. 根据权利要求1所述的除垢组合物，其中，所述螯合催化剂为氯化铵和亚硝酸钠的混合物。
  6. 根据权利要求5所述的除垢组合物，其中，以所述螯合催化剂的总重量计，氯化铵的含量为40-50wt％，亚硝酸钠的含量为50～60wt％。
  7. 根据权利要求1所述的除垢组合物，其中，所述螯合稳定剂选自柠檬酸钠、乙酸钠、甲酸钠和葡萄糖酸钠中的一种或多种。
  8. 根据权利要求1所述的除垢组合物，其中，所述渗透分散剂选自聚乙二醇PEG-600、脂肪醇聚氧乙烯醚硫酸钠、脂肪醇聚氧乙烯醚和石油磺酸盐中的一种或多种。
  9. 根据权利要求8所述的除垢组合物，其中，所述渗透分散剂为聚乙二醇PEG-600和石油磺酸盐的混合物；
    优选地，以所述渗透分散剂的总重量计，聚乙二醇PEG-600的含量为40～50wt％，石油磺酸盐的含量为50～60wt％。
  10. 根据权利要求1所述的除垢组合物，其中，所述pH调节剂选自氢氧化钠、氨水和氢氧化钾中的一种或多种，优选为氢氧化钠。
  11. 一种除垢剂的制备方法，其特征在于，所述制备方法包括：
    在搅拌条件下，将多氨基多酸螯合剂、增效剂、螯合催化剂和螯合稳定剂与水进行第一混合，得到第一混合物；
    在所述第一混合物中加入pH调节剂和渗透分散剂，进行第二混合，得到除垢剂；
    其中，所述除垢组合物的pH值为7～8；所述多氨基多酸螯合剂具有式I所示结构：
    式I中，R1为二烷基氨基、烷基氨基、氨基、羟基、烷氧基、酰胺基、酰氧基、羧基甲基或羧基。
  12. 根据权利要求11所述的制备方法，其中，按重量份计，多氨基羧酸螯合剂10～15份，增效剂1～2份，螯合催化剂0.5～1份，螯合稳定剂0.5～1份，渗透分散剂0.5～1份，pH调节剂5～10份和溶剂70～82.5份。
  13. 由权利要求11或12所述的制备方法制得的除垢剂。
  14. 权利要求1-10中任意一项所述的除垢组合物或权利要求13所述的除垢剂在油气井中的应用。
  15. 根据权利要求14所述的应用，其中，所述油气井的井内温度为80～180℃，优选为120～180℃。
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