CN108641695B - Corrosion inhibition bactericide for shale gas field - Google Patents
Corrosion inhibition bactericide for shale gas field Download PDFInfo
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- CN108641695B CN108641695B CN201810605163.0A CN201810605163A CN108641695B CN 108641695 B CN108641695 B CN 108641695B CN 201810605163 A CN201810605163 A CN 201810605163A CN 108641695 B CN108641695 B CN 108641695B
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- 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
- C09K8/54—Compositions for in situ inhibition of corrosion in boreholes or wells
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
- A01N35/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical containing aliphatically bound aldehyde or keto groups, or thio analogues thereof; Derivatives thereof, e.g. acetals
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
- A01N57/20—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing acyclic or cycloaliphatic radicals
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/32—Anticorrosion additives
Abstract
The invention discloses a corrosion inhibition bactericide for a shale gas field, which comprises the following components in parts by weight: 2-16 parts of amido oligomer, 15-30 parts of aldehyde, 15-30 parts of tetrakis hydroxymethyl phosphonium sulfate, 2-5 parts of alkylphenol polyoxyethylene OP-10 and 40-63 parts of water; wherein the amido oligomer is copolymerized by acrylamide, sodium acrylate and alkyl allyl quaternary ammonium salt. Compared with the prior art, the corrosion inhibition bactericide has the characteristics of long effective period, low consumption and good corrosion inhibition and sterilization effects, can be used for corrosion inhibition and sterilization of shale gas collection gas pipelines and water pipelines, sterilization and corrosion control of water and produced water for pressure test of oil and gas field pipelines, and has extremely strong killing effects on anaerobic bacteria and oxygen bacteria.
Description
Technical Field
The invention belongs to the technical field of oil and gas gathering and transportation of shale gas fields, and particularly relates to a corrosion inhibition bactericide for a shale gas field.
Background
In the development process of the shale gas field, bacteria can be brought into a production system by injecting water, drilling fluid, fracturing fluid and the like into the ground, from the production of shale gas at home and abroad, most shale gas fields can explode bacterial corrosion after 1-2 years of production, and pipelines begin to corrode and perforate after 1.5 years of production to lose effectiveness.
In the face of severe bacterial corrosion of shale gas fields, bactericides need to be filled for a long time to kill bacteria. Meanwhile, the produced liquid of the shale gas field contains residual acid and CO2And the corrosive media have strong corrosivity on underground pipe columns and ground gathering and transportation, and can cause pipeline corrosion. From the development experience of foreign shale gas fields, the production system has a plurality of bacteria, although the commonly used bactericide for water treatment has a killing effect on some bacteria, other bacteria can easily generate drug resistance on the bactericide, and the sterilizing effect cannot meet the field requirement. Meanwhile, due to the characteristic of long-term low yield of a single well, the shale gas field needs to adhere to the principle of low-cost development. The corrosion inhibition bactericide is added, so that the aims of corrosion prevention and bacteria control can be effectively and economically achieved.
Therefore, the filling of the corrosion-inhibiting bactericide can become a necessary process for many shale gas fields at home and abroad.
Disclosure of Invention
The invention aims to solve the problems of bacterial corrosion and electrochemical corrosion in the low-cost development process of shale gas fields, and provides a corrosion-inhibiting bactericide for sterilizing and controlling corrosion of shale gas field gathering and transportation pipelines or produced water.
At present, corrosion inhibition products for water treatment of oil and gas fields comprise quaternary ammonium salts, amides, imidazolines and other organic compounds containing N, P, S, and also comprise part of inorganic corrosion inhibitors. The amide makes the electric potential of metal iron shift forward, the alkyl long chain of alkyl allyl ammonium makes the corrosion inhibitor molecule have hydrophobicity, and proper molecular weight control can increase the corrosion inhibition performance of the polymer. The commonly used sterilization products include quaternary ammonium salts, diquaternary ammonium salts, polyquaternary ammonium salts, quaternary phosphine salts, aldehydes and some heterocyclic compounds. The aldehyde can kill all microorganisms in an oil and gas production system, but most of the aldehyde with good sterilization effect has higher price, and is matched with tetrakis hydroxymethyl phosphonium sulfate and amide oligomer for use, so that the sterilization cost can be reduced, and the aldehyde and the corrosion inhibitor molecule have a synergistic effect to improve the corrosion control effect. Therefore, the synthesized amide oligomer is mixed with aldehyde and tetrakis (hydroxymethyl) phosphonium sulfate from the aspects of improving economic benefit and corrosion control efficiency, so that the efficiency of the corrosion inhibitor can be improved, and the solution has better sterilization effect.
The invention provides a corrosion inhibition bactericide for a shale gas field, which comprises the following components in parts by weight:
according to an embodiment of the corrosion inhibition bactericide for the shale gas field, the corrosion inhibition bactericide for the shale gas field comprises the following components in parts by weight:
according to an embodiment of the corrosion inhibition bactericide for the shale gas field, the corrosion inhibition bactericide for the shale gas field comprises the following components in parts by weight:
the amido oligomer is obtained by copolymerizing acrylamide, sodium acrylate and alkyl allyl quaternary ammonium salt, the molecular weight Mn of the amido oligomer is 600-2500, preferably 1200, and the alkyl carbon chain length of the alkyl allyl quaternary ammonium salt is C8-C16.
Specifically, the amido oligomer is synthesized by dissolving sodium acrylate, acrylamide and alkyl allyl quaternary ammonium salt in distilled water according to a certain proportion, and adding a free radical initiator for polymerization under the conditions of stirring and nitrogen protection. As the molecular weight of the polymer increases, the viscosity increases for the same percentage of oligomer and solubility decreases, resulting in reduced corrosion inhibition performance. The corrosion inhibition effect of controlling the molecular weight of the corrosion inhibitor to be 600-2500 is better, and is better at about 1200. The amido oligomer synthesized by the method has the advantages of convenient raw material source, simple synthesis method and controllable cost.
In the corrosion inhibition bactericide for the shale gas field, the aldehyde is one or more of formaldehyde, acetaldehyde, propionaldehyde and glutaraldehyde.
Compared with the prior art, the corrosion inhibition bactericide has the characteristics of low consumption, good corrosion inhibition effect and good sterilization effect, can be used for sterilization and corrosion control of a downhole tubular column of a shale gas field, a ground gathering and transportation pipeline and a produced water pipeline, and can also be used for corrosion control and sterilization of pipelines of other types of oil fields and gas fields.
Detailed Description
All of the features disclosed in this specification, or all of the steps in any method or process so disclosed, may be combined in any combination, except combinations of features and/or steps that are mutually exclusive.
Any feature disclosed in this specification may be replaced by alternative features serving equivalent or similar purposes, unless expressly stated otherwise. That is, unless expressly stated otherwise, each feature is only an example of a generic series of equivalent or similar features.
The corrosion inhibiting bactericide for shale gas field of the present invention is further described with reference to the following specific examples.
Example 1:
the corrosion inhibition bactericide for the shale gas field comprises the following components in parts by weight:
wherein, the alkyl allyl quaternary ammonium salt in the amido oligomer is dodecyl dimethyl allyl ammonium chloride, the molecular weight of the amido oligomer is 1210, and the aldehyde is glutaraldehyde.
Experimental example 1:
preparing a corresponding culture medium according to SY/T0532-plus 2012 standard of the bacteria analysis method for the injected water in the oil and gas field, and measuring the sulfate reducing bacteria in the water sample to be 4.5 × 10 by counting by using an absolute dilution method3The count/mL of saprophytic bacteria is 1.5 × 103The number of iron bacteria per mL is 1.1 × 103The total number of bacteria is 7.1 × 10 per mL3one/mL.
The corrosion-inhibiting bactericide of example 1 was used, and the bactericide was injected into the water sample at room temperature and sterilized for 4 hours. And (4) injecting the sterilized water sample and the blank sample into a test bottle, standing for 7 days at room temperature, and testing the number of bacteria in the water sample. The results of the bacterial tests are shown in table 1:
TABLE 1 Sterilization Effect of different concentrations of Corrosion-inhibiting Fungicide (example 1)
As can be seen from Table 1, the bacteria in the produced water of shale gas field were all killed at 80mg/L concentration of the bactericide.
Experimental example 2:
the corrosion inhibition bactericide of example 1 is used, the concentration is 80mg/L, a 20# steel sample is used for carrying out a corrosion test at normal temperature and normal pressure, the test water is the shale gas field produced water of the experiment example 1, and the results are shown in Table 2:
TABLE 2 Corrosion inhibition Effect of the corrosion inhibiting bactericide of example 1
The corrosion-inhibiting bactericide of example 1 is used, the concentration is 80mg/L, the water used for the test is the shale gas field produced water of the experiment example 1, and the bactericidal effect is shown in Table 3:
TABLE 3 fungicidal Effect of the corrosion-inhibiting fungicides of example 1
The experimental results in tables 2 and 3 show that the corrosion-inhibiting bactericide has good corrosion inhibition and sterilization effects on the shale gas produced water.
Example 2:
the amido oligomer is synthesized by a free radical copolymerization method. Neutralizing AA (pH 8-9) with NaOH to form sodium acrylate (NaAA), and then adding n (am): n (naaa): n (C16DMAAC) ═ 84.25: 15: 0.75 collectively weighed 40.00 grams of monomer, where AM is acrylamide and C16DMAAC is cetyldimethylallylammonium chloride. Dissolving weighed monomers in 400mL of secondary distilled water, transferring the monomers into a 500mL three-neck flask after the monomers are completely dissolved, introducing high-purity nitrogen for 30min under the stirring condition, adding an initiator according to 0.3% of the mass fraction of the monomers, continuously introducing the nitrogen for 30min, placing a reaction system in a constant-temperature water bath at 50 ℃, and stopping the reaction after reacting for a certain time. The polymer was granulated and dried to constant weight and the viscosity average molecular weight of the polymer was determined by five point dilution. By controlling the reaction time, amide oligomers with different molecular weights are prepared, the corrosion inhibition performance of the amide oligomers is respectively tested by adopting the water sample of the produced water of the shale gas field in Sichuan as a corrosion medium, and the test results are shown in Table 4.
TABLE 4 evaluation results of corrosion inhibition Properties of amide oligomers of different molecular weights (unit: mm/a)
Note: "/" indicates that the polymer did not dissolve well.
The corrosion inhibition performance test result shows that the molecular weight is too small, and the corrosion inhibition performance is poor; the dissolution difficulty of the polymer with large concentration due to overlarge molecular weight affects the corrosion inhibition performance. When the molecular weight of the amido oligomer is about 1200 and the concentration of the polymer reaches more than 8 percent, the oligomer has good corrosion inhibition performance.
Example 3:
wherein the alkyl allyl quaternary ammonium salt in the amide oligomer is cetyl dimethyl allyl ammonium chloride, and the molecular weight of the amide oligomer is 2070.
Test example 3:
the water sample of the produced water of a certain shale gas field in Sichuan is according to oil gasPreparing a corresponding culture medium by adopting an absolute dilution method standard SY/T0532-one 2012 of a field injection water bacterial analysis method, and measuring that the sulfate reducing bacteria in a water sample is 4.5 × 10 by utilizing the absolute dilution method3The count/mL of saprophytic bacteria is 1.5 × 103The number of iron bacteria per mL is 1.1 × 103The total number of bacteria is 7.1 × 10 per mL3one/mL.
The corrosion inhibiting bactericide of example 3 was used at a concentration of 70mg/L, and the results of the corrosion test are shown in Table 5:
TABLE 5 Corrosion inhibition Effect of the corrosion inhibiting bactericide of example 3
The corrosion-inhibiting bactericide of example 3 was used at a concentration of 70mg/L, and the bactericidal effect is shown in Table 6:
TABLE 6 fungicidal Effect of the corrosion-inhibiting bactericide of example 3
The experimental results in tables 3 and 4 show that the corrosion-inhibiting bactericide disclosed by the invention has good corrosion inhibition and bactericidal effects on the shale gas produced water.
Example 4:
wherein, the alkyl allyl quaternary ammonium salt in the amido oligomer is tetradecyl dimethyl allyl ammonium chloride, and the molecular weight of the amido oligomer is 1620.
Preparing a corresponding culture medium according to SY/T0532-2012 standard of the bacterial analysis method for the injected water in the oil and gas field, and measuring the sulfate reducing bacteria in the water sample to be 5 × 10 by counting by using an absolute dilution method3Per mL, saprophyticThe number of the bacteria is 2.2 × 103The number of iron bacteria per mL is 1.5 × 103The total number of bacteria is 8.7 × 10 per mL3one/mL.
The corrosion-inhibiting bactericide of example 4 was used, and the bactericide was injected into the water sample at room temperature and sterilized for 4 hours. And (4) injecting the sterilized water sample and the blank sample into a test bottle, standing for 7 days at room temperature, and testing the number of bacteria in the water sample. The results of the bacterial testing are shown in table 7:
TABLE 7 fungicidal effectiveness of different concentrations of the corrosion-inhibiting fungicides (example 4)
When the concentration of the corrosion inhibition bactericide reaches 80mg/L, the number of bacteria measured in the solution is only 2, and the sterilizing effect is good.
Comparative example 1:
producing a water sample from a shale gas field in Sichuan, placing for 30 days, preparing a corresponding culture medium according to SY/T0532 + 2012 standard of an analysis method for bacteria in injected water in an oil and gas field, and measuring the content of sulfate reducing bacteria in the water sample to be 7.8 × 10 by counting by using an absolute dilution method3The bacterial count/mL and saprophytic bacteria count is 1.1 × 103The number of iron bacteria per mL is 0.5 × 103The total number of bacteria is 9.4 × 10 per mL3one/mL.
The corrosion-inhibiting bactericide of example 1 was used in combination with the commercial bactericide 1227, isothiazolinone, tetrakis (hydroxymethyl) phosphonium sulfate at the same concentration in the comparative test, all at 80 mg/L. The corrosion test results are shown in table 8, and the sterilization test results are shown in table 9.
TABLE 8 Corrosion Rate comparison of various biocides
TABLE 9 comparison of the bactericidal effects of different fungicides
As can be seen from tables 8 and 9, the corrosion-inhibiting bactericide provided by the invention has better corrosion inhibition and sterilization performance in the produced water of shale gas than the bactericide commonly used in the market.
Comparative example 2:
comparative tests were carried out using the shale gas field water sample of example 4 and the corrosion-inhibiting bactericide of example 4, together with 80mg/L of commercial bactericide 1227, isothiazolinone, tetrakis (hydroxymethyl) phosphonium sulfate, glutaraldehyde, and the results of the bactericidal tests are shown in Table 10, with 80mg/L of bactericide being added to the test solutions every 30 days.
TABLE 10 comparison of the fungicidal effectiveness of various fungicides
The test results in table 10 show that the broad-spectrum bactericide 1227, isothiazolinone, and tetrakis (hydroxymethyl) phosphonium sulfate, which are commonly used in oil and gas fields, all have good bactericidal effects in the initial stage of injection, but as the injection time increases, part of bacteria generate drug resistance, and the number of bacteria increases again. The aldehyde bactericide glutaraldehyde has a killing effect on all bacteria in the oil and gas field, and the sterilization effect in the whole test period is good. The corrosion inhibition bactericide of the embodiment 4 has a good bactericidal effect in the whole test period, and simultaneously, the addition of the glutaraldehyde and the tetrakis hydroxymethyl phosphonium sulfate can effectively reduce the cost of the bactericide on the basis of the same bactericidal effect, thereby meeting the dual requirements of long-term bactericide injection and low-cost development of the shale gas field.
In conclusion, the corrosion inhibition bactericide has the characteristics of low cost, low consumption and good corrosion inhibition and sterilization effects, and can be used for sterilization and corrosion control of pipeline produced water, pressure test water, injected water and the like of shale gas fields and other oil and gas fields.
The invention is not limited to the foregoing embodiments. The invention extends to any novel feature or any novel combination of features disclosed in this specification and any novel method or process steps or any novel combination of features disclosed.
Claims (7)
1. The corrosion inhibition bactericide for the shale gas field is characterized by comprising the following components in parts by weight:
wherein the amido oligomer is obtained by copolymerizing acrylamide, sodium acrylate and alkyl allyl quaternary ammonium salt.
2. The shale gas field corrosion inhibition bactericide as claimed in claim 1, which comprises the following components in parts by weight:
wherein the amido oligomer is obtained by copolymerizing acrylamide, sodium acrylate and alkyl allyl quaternary ammonium salt.
3. The shale gas field corrosion inhibition bactericide as claimed in claim 1, which comprises the following components in parts by weight:
wherein the amido oligomer is obtained by copolymerizing acrylamide, sodium acrylate and alkyl allyl quaternary ammonium salt.
4. The corrosion-inhibiting bactericide for the shale gas field according to any one of claims 1 to 3, wherein the amide-based oligomer has a molecular weight Mn of 600 to 2500.
5. The corrosion inhibiting bactericide for shale gas fields according to any one of claims 1 to 3, wherein the amide-based oligomer has a molecular weight Mn of 1200.
6. The corrosion inhibiting and killing agent for shale gas fields as claimed in any one of claims 1 to 3, wherein the alkyl carbon chain length of the alkyl allyl ammonium is C8-C16.
7. The corrosion inhibiting bactericide for shale gas fields according to any one of claims 1 to 3, wherein the aldehyde is one or more of formaldehyde, acetaldehyde, propionaldehyde and glutaraldehyde.
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| CN112646558B (en) * | 2020-12-18 | 2022-08-16 | 成都劳恩普斯科技有限公司 | Ecological safety sterilization corrosion inhibitor special for shale gas pipeline and preparation method thereof |
| CN113563856A (en) * | 2021-08-04 | 2021-10-29 | 东方宝麟科技发展(北京)有限公司 | Pipeline corrosion prevention and inhibition bactericide, preparation method and application thereof |
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