CN103849365B - A kind of inhibitor for oil well sulfate scale and Synthesis and applications thereof - Google Patents

A kind of inhibitor for oil well sulfate scale and Synthesis and applications thereof Download PDF

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CN103849365B
CN103849365B CN201410108953.XA CN201410108953A CN103849365B CN 103849365 B CN103849365 B CN 103849365B CN 201410108953 A CN201410108953 A CN 201410108953A CN 103849365 B CN103849365 B CN 103849365B
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inhibitor
present
composition
sulfate scale
water
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CN103849365A (en
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任呈强
刘丽
郑云萍
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Southwest Petroleum University
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/52Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
    • C09K8/528Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning inorganic depositions, e.g. sulfates or carbonates
    • EFIXED CONSTRUCTIONS
    • E21EARTH OR ROCK DRILLING; MINING
    • E21BEARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B37/00Methods or apparatus for cleaning boreholes or wells
    • E21B37/06Methods or apparatus for cleaning boreholes or wells using chemical means for preventing or limiting, e.g. eliminating, the deposition of paraffins or like substances

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Abstract

The invention discloses a kind of inhibitor for oil well sulfate scale and Synthesis and applications thereof.The weight percent that the composition that this inhibitor contains and each composition account for inhibitor is: polycarboxylic acid polymer 35% ~ 45%; Poly aspartic acid 25% ~ 35%; Hydrolytic polymaleic anhydride 10% ~ 15%; 2-thiol group tetrahydroglyoxaline 15% ~ 20%; Ethylene diamine tetra methylene phosphonic acid sodium 2% ~ 5%.Inhibitor of the present invention is liquid; To BaSO 4and SrSO 4the inhibition of fouling is good; Low containing phosphine amount, component is easily biodegradable, good environmental protection; Temperature limit is wide, and use temperature can up to 100 DEG C.

Description

A kind of inhibitor for oil well sulfate scale and Synthesis and applications thereof
Technical field
The present invention relates to a kind of inhibitor for oil well sulfate scale and Synthesis and applications thereof.
Background technology
In oil mining process, on the one hand, when stratum corrosion ion, inject after the ion that carries of water enters local water, cause water intermediate ion incompatible and produce precipitation, on the other hand, when temperature, pressure and other parameters change cause local water intermediate ion to balance destruction, Cucumber is made to exceed solubility product and deposit.The material of these depositions is called as dirt, and oil well fouling is divided into carbonate scale and sulfate scale by the component according to dirt, and the former mainly contains CaCO 3and MgCO 3, the latter mainly contains BaSO 4and SrSO 4.When after oil well fouling, reservoir can be injured, block pit shaft or cause underdeposit corrosion, seriously reduce production efficiency, and increase production cost.
Adopting chemical agent to control fouling is the major measure used at present, and the inhibitor developed for carbonate scale is very many, but less for the inhibitor of sulfate scale.Sulfate scale is once generate, and its dirt is hard, and is difficult to by acid-soluble erosion, is be difficult to removing, therefore how effectively suppresses Ba 2+, Sr 2+with SO 4 2-fouling is technical problem urgently to be resolved hurrily at present.
Summary of the invention
In order to solve the problems of the technologies described above, the invention provides a kind of inhibitor for oil well sulfate scale and Synthesis and applications thereof
The weight percent that the composition that contains for the inhibitor of oil well sulfate scale provided by the invention and each composition account for inhibitor is:
Polycarboxylic acid polymer 35% ~ 45%;
Poly aspartic acid 25% ~ 35%;
Hydrolytic polymaleic anhydride 10% ~ 15%;
2-thiol group tetrahydroglyoxaline 15% ~ 20%;
Ethylene diamine tetra methylene phosphonic acid sodium 2% ~ 5%.
Preferably, the weight percent that the composition that above-mentioned inhibitor contains and each composition account for inhibitor is:
Polycarboxylic acid polymer 38%;
Poly aspartic acid 30%;
Hydrolytic polymaleic anhydride 12%;
2-thiol group tetrahydroglyoxaline 16%;
Ethylene diamine tetra methylene phosphonic acid sodium 4%.
Preferably, described polycarboxylic acid polymer is MALEIC ANHYDRIDE/vinylformic acid/sodium allyl sulfonate/methyl acrylate copolymer, vinylformic acid-2-acrylamide-2-methyl propane sulfonic multipolymer or acrylic acid/esters/co-polymer of sulfonate.
The invention provides the preparation method of above-mentioned inhibitor, according to described amount, each composition is mixed.
The invention provides the application of above-mentioned inhibitor: by water-soluble for described inhibitor, be mixed with the aqueous solution, then annotate in oil well, filling rate calculates by water production rate, the concentration making inhibitor be dissolved in local water in well is 30mg/L ~ 600mg/L, adopts continuous dosing method to carry out.
As optimal technical scheme, by water-soluble for described inhibitor, being mixed with total concn is 50 ~ 500g/L aqueous solution.
Inhibitor for oil well sulfate scale of the present invention has following Advantageous Effects:
1, inhibitor of the present invention is liquid; To BaSO 4the inhibition of fouling is good; To SrSO 4the inhibition of fouling is good.
2, inhibitor of the present invention is low containing phosphine amount, and component is easily biodegradable, good environmental protection;
3, inhibitor temperature limit of the present invention is wide, and use temperature can up to 100 DEG C.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described, can better understand the present invention and can be implemented, but illustrated embodiment is not as a limitation of the invention to make those skilled in the art.
The present invention is for a kind of inhibitor of oil well sulfate scale, and the weight percent that described inhibitor accounts for described inhibitor containing, for example lower composition and each composition is:
Polycarboxylic acid polymer 35% ~ 45%;
Poly aspartic acid 25% ~ 35%;
Hydrolytic polymaleic anhydride 10% ~ 15%;
2-thiol group tetrahydroglyoxaline 15% ~ 20%;
Ethylene diamine tetra methylene phosphonic acid sodium 2% ~ 5%.
Wherein polycarboxylic acid polymer is MALEIC ANHYDRIDE/vinylformic acid/sodium allyl sulfonate/methyl acrylate copolymer, vinylformic acid-2-acrylamide-2-methyl propane sulfonic multipolymer or acrylic acid/esters/co-polymer of sulfonate.
In component, polycarboxylic acid polymer, poly aspartic acid, hydrolytic polymaleic anhydride and ethylene diamine tetra methylene phosphonic acid sodium all can be used for the generation suppressing dirt, wherein hydrolytic polymaleic anhydride makes divalent-metal ion form stable soluble chelating thing by sequestering action, improve ion permissible concentration, poly aspartic acid is by stoping structure in plane of crystal adsorption, polycarboxylic acid polymer disperses crystallite by adsorbing the fouling crystallite of identical charges under electrostatic repulsion effect, stops collision to form dirt.Owing to suppressing the mechanism of dirt there are differences, therefore good synergy can be played.Meanwhile, sulfonic group, carboxylic acid group and amino isopolarity contained by this several material are comparatively strong, and very well, 2-thiol group tetrahydroglyoxaline is good tensio-active agent, therefore this formula is soluble in local water, plays good restraining effect to scale-forming ion in water for dispersiveness and wetting ability.2-thiol group tetrahydroglyoxaline or a kind of inhibiter, slow down the corrodibility of local water to metal tubing string.
When implementing, the inhibitor of oil well sulfate scale of the present invention is dissolved in the water by mass percentage successively, be configured to the total concn of 50 ~ 500g/L, during Xiang Jingzhong filling, filling rate calculates by water production rate, the concentration making inhibitor be dissolved in local water in well is 30mg/L ~ 600mg/L, adopts continuous dosing method to carry out.
Sulfate scale inhibitor advantage of the present invention is: 1, solubility property is good, easily constructs; 2, to BaSO 4and SrSO 4fouling has good suppression efficiency; 3, the feature of environmental protection is good.4, use temperature wide ranges.
Specific embodiment:
Embodiment 1
The sulfate scale inhibitor of the present embodiment, the weight percent accounting for inhibitor containing, for example lower composition and each composition is:
Vinylformic acid-2-acrylamide-2-methyl propane sulfonic multipolymer 38%;
Poly aspartic acid 30%;
Hydrolytic polymaleic anhydride 12%;
2-thiol group tetrahydroglyoxaline 16%;
Ethylene diamine tetra methylene phosphonic acid sodium 4%;
Wherein, vinylformic acid-2-acrylamide-2-methyl propane sulfonic multipolymer is the AA/AMPS purchased from Shandong Taihe Water Treatment Co., Ltd..
The preparation method of above-mentioned sulfate scale inhibitor, step is as follows: take each component according to weight percent, mixes and stirs.
The inhibition evaluation of the present embodiment sulfate scale inhibitor: test according to People's Republic of China's oil and gas industry standard " scale inhibitor for oilfield method of evaluating performance (SY/T5673-93) ", probe temperature is 70 DEG C.Adopt atomic spectrophotometer test barium strontium ion concentration, and according to: the calculation formula specified in SY/T5673-93 calculates inhibiting rate (antiscaling rate).The implementation result of the present embodiment: BaSO 4and SrSO 4the inhibiting rate of fouling is respectively 94.0% and 94.4%.
In order to check the Applicable temperature scope of the present embodiment sulfate scale inhibitor, the present embodiment, under different probe temperatures, carries out testing (probe temperature is different from the temperature in this standard) according to People's Republic of China's oil and gas industry standard " scale inhibitor for oilfield method of evaluating performance (SY/T5673-93) ".After tested and calculate, at 25 DEG C, the inhibition of the sulfate scale inhibitor of the present embodiment is: BaSO 4and SrSO 4the inhibiting rate of fouling is respectively 97.2% and 96.7%; At 100 DEG C, the inhibition of the sulfate scale inhibitor of the present embodiment is: BaSO 4and SrSO 4the inhibiting rate of fouling is respectively 91.4% and 91.8%.To sum up, can find out that the inhibitor temperature limit of the present embodiment is very wide.
When reality is implemented, the inhibitor of oil well sulfate scale of the present invention is dissolved in the water by mass percentage successively, be configured to the total concn (namely dissolving 50 ~ 500g inhibitor in 1L water) of 50 ~ 500g/L, during Xiang Jingzhong filling, filling rate calculates by water production rate, the concentration making inhibitor be dissolved in local water in well is 30mg/L ~ 600mg/L, adopts continuous dosing method to carry out.Result shows, and the inhibitor of the present embodiment is to BaSO 4and SrSO 4fouling has good suppression efficiency.
Embodiment 2
The sulfate scale inhibitor of the present embodiment, the weight percent accounting for inhibitor containing, for example lower composition and each composition is:
MALEIC ANHYDRIDE/vinylformic acid/sodium allyl sulfonate/methyl acrylate copolymer 45%;
Poly aspartic acid 25%;
Hydrolytic polymaleic anhydride 10%;
2-thiol group tetrahydroglyoxaline 15%;
Ethylene diamine tetra methylene phosphonic acid sodium 5%;
Wherein, MALEIC ANHYDRIDE/vinylformic acid/sodium allyl sulfonate/methyl acrylate copolymer can be prepared according to synthetic method disclosed in " the synthesis and property evaluation of novel barium (strontium) Scale inhibitors CD-1 " (Chongqing University of Science and Technology journal (natural science edition), the 3rd phase in 2009).
The preparation method of above-mentioned sulfate scale inhibitor, step is as follows: take each component according to weight percent, mixes and stirs.
The inhibition evaluation of the present embodiment sulfate scale inhibitor: test according to People's Republic of China's oil and gas industry standard " scale inhibitor for oilfield method of evaluating performance (SY/T5673-93) ", probe temperature 70 DEG C.Adopt atomic spectrophotometer test barium strontium ion concentration, and according to: the calculation formula specified in SY/T5673-93 calculates inhibiting rate (antiscaling rate).
The implementation result of the present embodiment: BaSO 4and SrSO 4the inhibiting rate of fouling is respectively 87.2% and 89.5%.
In order to check the Applicable temperature scope of the present embodiment sulfate scale inhibitor, the present embodiment, under different probe temperatures, carries out testing (probe temperature is different from the temperature in this standard) according to People's Republic of China's oil and gas industry standard " scale inhibitor for oilfield method of evaluating performance (SY/T5673-93) ".After tested and calculate, at 25 DEG C, the inhibition of the sulfate scale inhibitor of the present embodiment is: BaSO 4and SrSO 4the inhibiting rate of fouling is respectively 92.3% and 91.6%; At 100 DEG C, the inhibition of the sulfate scale inhibitor of the present embodiment is: BaSO 4and SrSO 4the inhibiting rate of fouling is respectively 85.2% and 85.1%.To sum up, can find out that the inhibitor temperature limit of the present embodiment is very wide.
When reality is implemented, the inhibitor of oil well sulfate scale of the present invention is dissolved in the water by mass percentage successively, be configured to the total concn of 50 ~ 500g/L, during Xiang Jingzhong filling, filling rate calculates by water production rate, the concentration making inhibitor be dissolved in local water in well is 30mg/L ~ 600mg/L, adopts continuous dosing method to carry out.Result shows, and the inhibitor of the present embodiment is to BaSO 4and SrSO 4fouling has good suppression efficiency.
Embodiment 3
The sulfate scale inhibitor of the present embodiment, the weight percent accounting for inhibitor containing, for example lower composition and each composition is:
Vinylformic acid-2-acrylamide-2-methyl propane sulfonic multipolymer 35%;
Poly aspartic acid 35%;
Hydrolytic polymaleic anhydride 15%;
2-thiol group tetrahydroglyoxaline 10%;
Ethylene diamine tetra methylene phosphonic acid sodium 5%;
Wherein, vinylformic acid-2-acrylamide-2-methyl propane sulfonic multipolymer is the AA/AMPS purchased from Shandong Taihe Water Treatment Co., Ltd..
The preparation method of above-mentioned sulfate scale inhibitor, step is as follows: take each component according to weight percent, mixes and stirs.
The inhibition evaluation of the present embodiment sulfate scale inhibitor: test according to People's Republic of China's oil and gas industry standard " scale inhibitor for oilfield method of evaluating performance (SY/T5673-93) ", probe temperature 70 DEG C.Adopt atomic spectrophotometer test barium strontium ion concentration, and according to: the calculation formula specified in SY/T5673-93 calculates inhibiting rate (antiscaling rate).
The implementation result of the present embodiment: BaSO 4and SrSO 4the inhibiting rate of fouling is respectively 92.60% and 90.00%.
In order to check the Applicable temperature scope of the present embodiment sulfate scale inhibitor, the present embodiment, under different probe temperatures, carries out testing (probe temperature is different from the temperature in this standard) according to People's Republic of China's oil and gas industry standard " scale inhibitor for oilfield method of evaluating performance (SY/T5673-93) ".After tested and calculate, at 25 DEG C, the inhibition of the sulfate scale inhibitor of the present embodiment is: BaSO 4and SrSO 4the inhibiting rate of fouling is respectively 95.6% and 94.4%; At 100 DEG C, the inhibition of the sulfate scale inhibitor of the present embodiment is: BaSO 4and SrSO 4the inhibiting rate of fouling is respectively 90.0% and 89.5%.To sum up, can find out that the inhibitor temperature limit of the present embodiment is very wide.
When reality is implemented, the inhibitor of oil well sulfate scale of the present invention is dissolved in the water by mass percentage successively, be configured to the total concn of 50 ~ 500g/L, during Xiang Jingzhong filling, filling rate calculates by water production rate, the concentration making inhibitor be dissolved in local water in well is 30mg/L ~ 600mg/L, adopts continuous dosing method to carry out.Result shows, and the inhibitor of the present embodiment is to BaSO 4and SrSO 4fouling has good suppression efficiency.
Embodiment 4
The sulfate scale inhibitor of the present embodiment, the weight percent accounting for inhibitor containing, for example lower composition and each composition is:
Acrylic acid/esters/co-polymer of sulfonate 40%;
Poly aspartic acid 30%;
Hydrolytic polymaleic anhydride 12%;
2-thiol group tetrahydroglyoxaline 16%;
Ethylene diamine tetra methylene phosphonic acid sodium 2%;
Wherein, acrylic acid/esters/co-polymer of sulfonate is the TH-613 acrylic acid/esters/sulfonate terpolymer purchased from Shandong Taihe Water Treatment Co., Ltd..
The preparation method of above-mentioned sulfate scale inhibitor, step is as follows: take each component according to weight percent, mixes and stirs.
The inhibition evaluation of the present embodiment sulfate scale inhibitor: test according to People's Republic of China's oil and gas industry standard " scale inhibitor for oilfield method of evaluating performance (SY/T5673-93) ", probe temperature 70 DEG C.Adopt atomic spectrophotometer test barium strontium ion concentration, and according to: the calculation formula specified in SY/T5673-93 calculates inhibiting rate (antiscaling rate).
The implementation result of the present embodiment: BaSO 4and SrSO 4the inhibiting rate of fouling is respectively 90.1% and 91.5%.
In order to check the Applicable temperature scope of the present embodiment sulfate scale inhibitor, the present embodiment, under different probe temperatures, carries out testing (probe temperature is different from the temperature in this standard) according to People's Republic of China's oil and gas industry standard " scale inhibitor for oilfield method of evaluating performance (SY/T5673-93) ".After tested and calculate, at 25 DEG C, the inhibition of the sulfate scale inhibitor of the present embodiment is: BaSO 4and SrSO 4the inhibiting rate of fouling is respectively 94.3% and 95.6%; At 100 DEG C, the inhibition of the sulfate scale inhibitor of the present embodiment is: BaSO 4and SrSO 4the inhibiting rate of fouling is respectively 89.4% and 89.7%.To sum up, can find out that the inhibitor temperature limit of the present embodiment is very wide.
When reality is implemented, the inhibitor of oil well sulfate scale of the present invention is dissolved in the water by mass percentage successively, be configured to the total concn of 50 ~ 500g/L, during Xiang Jingzhong filling, filling rate calculates by water production rate, the concentration making inhibitor be dissolved in local water in well is 30mg/L ~ 600mg/L, adopts continuous dosing method to carry out.Result shows, and the inhibitor of the present embodiment is to BaSO 4and SrSO 4fouling has good suppression efficiency.
Embodiment 5
The sulfate scale inhibitor of the present embodiment, the weight percent accounting for inhibitor containing, for example lower composition and each composition is:
Vinylformic acid-2-acrylamide-2-methyl propane sulfonic multipolymer 40%;
Poly aspartic acid 25%;
Hydrolytic polymaleic anhydride 10%;
2-thiol group tetrahydroglyoxaline 20%;
Ethylene diamine tetra methylene phosphonic acid sodium 5%;
Wherein, vinylformic acid-2-acrylamide-2-methyl propane sulfonic multipolymer is the AA/AMPS purchased from Shandong Taihe Water Treatment Co., Ltd..
The preparation method of above-mentioned sulfate scale inhibitor, step is as follows: take each component according to weight percent, mixes and stirs.
The inhibition evaluation of the present embodiment sulfate scale inhibitor: test according to People's Republic of China's oil and gas industry standard " scale inhibitor for oilfield method of evaluating performance (SY/T5673-93) ", probe temperature 70 DEG C.Adopt atomic spectrophotometer test barium strontium ion concentration, and according to: the calculation formula specified in SY/T5673-93 calculates inhibiting rate (antiscaling rate).
The implementation result of the present embodiment: BaSO 4and SrSO 4the inhibiting rate of fouling is respectively 91.4% and 91.7%.
In order to check the Applicable temperature scope of the present embodiment sulfate scale inhibitor, the present embodiment, under different probe temperatures, carries out testing (probe temperature is different from the temperature in this standard) according to People's Republic of China's oil and gas industry standard " scale inhibitor for oilfield method of evaluating performance (SY/T5673-93) ".After tested and calculate, at 20 DEG C, the inhibition of the sulfate scale inhibitor of the present embodiment is: BaSO 4and SrSO 4the inhibiting rate of fouling is respectively 96.7% and 96.3%; At 100 DEG C, the inhibition of the sulfate scale inhibitor of the present embodiment is: BaSO 4and SrSO 4the inhibiting rate of fouling is respectively 90.3% and 89.8%.To sum up, can find out that the inhibitor temperature limit of the present embodiment is very wide.
When reality is implemented, the inhibitor of oil well sulfate scale of the present invention is dissolved in the water by mass percentage successively, be configured to the total concn of 50 ~ 500g/L, during Xiang Jingzhong filling, filling rate calculates by water production rate, the concentration making inhibitor be dissolved in local water in well is 30mg/L ~ 600mg/L, adopts continuous dosing method to carry out.Result shows, and the inhibitor of the present embodiment is to BaSO 4and SrSO 4fouling has good suppression efficiency.
The above embodiment is only that protection scope of the present invention is not limited thereto in order to absolutely prove the preferred embodiment that the present invention lifts.The equivalent alternative or conversion that those skilled in the art do on basis of the present invention, all within protection scope of the present invention.Protection scope of the present invention is as the criterion with claims.

Claims (5)

1. for an inhibitor for oil well sulfate scale, it is characterized in that, the weight percent that its composition contained and each composition account for inhibitor is:
Polycarboxylic acid polymer 35% ~ 45%;
Poly aspartic acid 25% ~ 35%;
Hydrolytic polymaleic anhydride 10% ~ 15%;
2-thiol group tetrahydroglyoxaline 15% ~ 20%;
Ethylene diamine tetra methylene phosphonic acid sodium 2% ~ 5%;
Described polycarboxylic acid polymer is MALEIC ANHYDRIDE/vinylformic acid/sodium allyl sulfonate/methyl acrylate copolymer, vinylformic acid-2-acrylamide-2-methyl propane sulfonic multipolymer or acrylic acid/esters/co-polymer of sulfonate;
The weight percent sum that above-mentioned each composition accounts for inhibitor is 100%.
2. inhibitor according to claim 1, is characterized in that, the weight percent that its composition contained and each composition account for inhibitor is:
Polycarboxylic acid polymer 38%;
Poly aspartic acid 30%;
Hydrolytic polymaleic anhydride 12%;
2-thiol group tetrahydroglyoxaline 16%;
Ethylene diamine tetra methylene phosphonic acid sodium 4%.
3. the preparation method of the inhibitor described in claim 1 or 2, is characterized in that, is mixed by each composition according to described amount.
4. the application of the inhibitor described in claim 1 or 2, it is characterized in that, by water-soluble for described inhibitor, be mixed with the aqueous solution, then annotate in oil well, filling rate calculates by water production rate, and the concentration making inhibitor be dissolved in local water in well is 30mg/L ~ 600mg/L, adopts continuous dosing method to carry out.
5. application according to claim 4, is characterized in that, by water-soluble for described inhibitor, being mixed with total concn is 50 ~ 500g/L aqueous solution.
CN201410108953.XA 2014-03-21 2014-03-21 A kind of inhibitor for oil well sulfate scale and Synthesis and applications thereof Expired - Fee Related CN103849365B (en)

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CN104925968B (en) * 2015-07-07 2017-03-01 西南石油大学 A kind of salt tolerant high-temperature-resistant scale inhibitor and preparation method thereof
CN106675542A (en) * 2016-12-12 2017-05-17 西安天太石化科技有限公司 Multifunctional polyurethane injection enhancement agent for oil field
CN107983539A (en) * 2017-12-06 2018-05-04 中南大学 Application of the hydrolysis of polymaleic anhydride in Scheelite Flotation
CN108178343B (en) * 2018-01-15 2021-05-07 东北石油大学 Environment-friendly long-acting scale inhibitor for oil field and preparation method thereof
CN113429951B (en) * 2021-08-02 2023-02-28 浙江砉润科技有限公司 Biomass pollution-free oilfield blocking remover

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