CN115568480B - Plant-based composite bacteriostatic agent for oil field and preparation method and application thereof - Google Patents
Plant-based composite bacteriostatic agent for oil field and preparation method and application thereof Download PDFInfo
- Publication number
- CN115568480B CN115568480B CN202211181462.9A CN202211181462A CN115568480B CN 115568480 B CN115568480 B CN 115568480B CN 202211181462 A CN202211181462 A CN 202211181462A CN 115568480 B CN115568480 B CN 115568480B
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- China
- Prior art keywords
- plant
- based composite
- bacteriostat
- extract
- bacteriostatic agent
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- 239000002131 composite material Substances 0.000 title claims abstract description 177
- 239000000022 bacteriostatic agent Substances 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
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- 239000000419 plant extract Substances 0.000 claims abstract description 74
- 238000005260 corrosion Methods 0.000 claims abstract description 73
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- 241000894006 Bacteria Species 0.000 claims abstract description 41
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- 238000000034 method Methods 0.000 claims description 30
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- NLDDIKRKFXEWBK-AWEZNQCLSA-N gingerol Chemical compound CCCCC[C@H](O)CC(=O)CCC1=CC=C(O)C(OC)=C1 NLDDIKRKFXEWBK-AWEZNQCLSA-N 0.000 claims description 18
- JZLXEKNVCWMYHI-UHFFFAOYSA-N gingerol Natural products CCCCC(O)CC(=O)CCC1=CC=C(O)C(OC)=C1 JZLXEKNVCWMYHI-UHFFFAOYSA-N 0.000 claims description 18
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 28
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- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 4
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
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- UUIVKBHZENILKB-UHFFFAOYSA-N 2,2-dibromo-2-cyanoacetamide Chemical compound NC(=O)C(Br)(Br)C#N UUIVKBHZENILKB-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229930182555 Penicillin Natural products 0.000 description 1
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 description 1
- PLXBWHJQWKZRKG-UHFFFAOYSA-N Resazurin Chemical compound C1=CC(=O)C=C2OC3=CC(O)=CC=C3[N+]([O-])=C21 PLXBWHJQWKZRKG-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
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- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- LOKCTEFSRHRXRJ-UHFFFAOYSA-I dipotassium trisodium dihydrogen phosphate hydrogen phosphate dichloride Chemical compound P(=O)(O)(O)[O-].[K+].P(=O)(O)([O-])[O-].[Na+].[Na+].[Cl-].[K+].[Cl-].[Na+] LOKCTEFSRHRXRJ-UHFFFAOYSA-I 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- 238000002347 injection Methods 0.000 description 1
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- 239000002054 inoculum Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
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- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000001540 sodium lactate Substances 0.000 description 1
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- 235000011088 sodium lactate Nutrition 0.000 description 1
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- YIEDHPBKGZGLIK-UHFFFAOYSA-L tetrakis(hydroxymethyl)phosphanium;sulfate Chemical compound [O-]S([O-])(=O)=O.OC[P+](CO)(CO)CO.OC[P+](CO)(CO)CO YIEDHPBKGZGLIK-UHFFFAOYSA-L 0.000 description 1
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Classifications
-
- 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
- A01N65/00—Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
-
- 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
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
-
- 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
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
- A01N59/20—Copper
-
- 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
- A01N65/00—Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
- A01N65/40—Liliopsida [monocotyledons]
- A01N65/48—Zingiberaceae [Ginger family], e.g. ginger or galangal
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Abstract
The invention provides a plant-based composite bacteriostatic agent for an oil field, and a preparation method and application thereof, and belongs to the technical field of oilfield chemistry. The invention provides a plant-based composite bacteriostatic agent for oil fields, which comprises bimetallic nanoparticles and plant extracts; the bimetal nanoparticle includes nano silver and nano copper. The plant extract in the plant-based composite bacteriostatic agent provided by the invention can be used as a reducing agent and a dispersing agent of bimetallic nanoparticles and as a plant-based corrosion inhibitor; the bimetal nano particles have the functions of resisting and inhibiting bacteria and catalyzing corrosion inhibition of the plant extract carbon steel. The plant-based composite bacteriostat can effectively reduce the growth activity of sulfate reducing bacteria and the weight loss rate of carbon steel through the synergistic effect of plant extracts and the bimetallic nanoparticles, and can be applied to the anti-corrosion operation of oilfield pipelines to be beneficial to the safe performance of oilfield production.
Description
Technical Field
The invention belongs to the technical field of oilfield chemistry, and particularly relates to a plant-based composite bacteriostatic agent for an oilfield, and a preparation method and application thereof.
Background
Sulfate-reducing bacteria (SRB) are widely distributed in soil and water, and their enrichment and growth in oil pipelines produces H 2 S gas causes pitting and perforation of the pipe. Sulfide produced by bacterial metabolism has an important influence on oil reservoir acidification, and safety accidents such as pipeline perforation, economic loss, even casualties and the like caused by corrosion often occur in the development and production links of oil and gas fields. Chemical bactericides such as glutaraldehyde, dibromo-nitrilopropionamide (DBNPA), tetra (hydroxymethyl) phosphonium sulfate (THPS) and alkyl dimethyl benzyl ammonium chloride which are commonly used in the past show increasingly strong antibiotic resistance due to their instability under extreme environmental conditions in oil fields. Therefore, the development of new antibacterial agents that inhibit SRB growth is of great importance in ensuring safe production operations in oil and gas fields.
Disclosure of Invention
The invention aims to provide a plant-based composite bacteriostatic agent for an oil field, which can effectively inhibit growth of sulfate reducing bacteria and prevent corrosion of carbon steel pipelines of the oil field.
The invention provides a plant-based composite bacteriostatic agent for oil fields, which comprises bimetallic nanoparticles and plant extracts; the bimetal nanoparticle includes nano silver and nano copper.
Preferably, the bimetallic nanoparticle is produced from a combination of zero-valent silver and copper at the nanoscale; the atomic ratio of nano silver to nano copper in each bimetallic metal nanoparticle is 1:5-5:1.
Preferably, the particle size of the bimetal nanoparticle is 20-50 nm.
Preferably, the plant extract comprises a reducing active substance and a biosurfactant; the reducing active substance comprises gingerol; the biological surface active substance is a macromolecular active substance containing hydroxyl groups.
Preferably, the plant extract comprises ginger extract; the preparation method of the plant extract comprises the following steps: mixing plant raw materials with water for water extraction to obtain a primary water extract; and (3) defibrating the preliminary water extract to obtain a plant extract.
The invention provides a preparation method of the plant-based composite bacteriostat, which comprises the following steps:
mixing a silver ion solution and a copper ion solution to obtain a metal precursor solution;
and mixing the metal precursor solution with the plant extract to obtain the plant-based composite bacteriostatic agent.
Preferably, the molar concentration ratio of silver ions to copper ions in the metal precursor solution is (0.25 to 0.75): (0.25-0.75).
Preferably, the volume ratio of the metal precursor solution to the plant extract is 1-3:1-3; the molar concentration of silver ions in the metal precursor solution is 0.25-0.75 mmol/L, and the molar concentration of copper ions is 0.25-0.75 mmol/L.
Preferably, the metal precursor solution is mixed with the plant extract and then the temperature in the reaction system is kept at 75-95 ℃; the temperature maintaining time is 15-45 min.
The invention also provides application of the plant-based composite bacteriostatic agent in one or more of bacteriostasis, carbon steel corrosion inhibition and oilfield oil pipeline corrosion inhibition.
The beneficial effects are that:
the invention provides a plant-based composite bacteriostatic agent for oil fields, which comprises bimetallic nanoparticles and plant extracts; the bimetal nanoparticle includes nano silver and nano copper. The plant extract in the plant-based composite bacteriostatic agent can be used as a reducing agent and a dispersing agent of the bimetal nano particles, so that the bimetal nano particles are prevented from being aggregated into particles with larger sizes, the uniform dispersion of the bimetal nano particles in a small-particle-size alloy form is realized, and the plant extract can also be used as a corrosion inhibitor adsorbed on the surface of carbon steel to slow down or even prevent the corrosion of the carbon steel; the bimetal nano particles are compounded by adopting two metal nano particles, the geometry and the electronic structure of the nano simple substance metal particles can be adjusted by adding the two metals, so that the nano simple substance metal particles have multi-metal characteristics in the aspects of size, shape, zeta potential, surface energy and the like, the adsorption process of the plant extract on the surface of the carbon steel is enhanced by utilizing the high surface energy of the bimetal nano particles, so that the catalysis effect of the bimetal nano particles on the slow release effect of the plant extract is improved, and on the other hand, the multi-metal characteristics of the bimetal nano particles are beneficial to the effective interaction of the bimetal nano particles and bacterial cell membranes, so that the damage of a host immune system, active oxygen generation, protein dysfunction and DNA damage are caused. The bimetal nano particles are used as antibacterial active ingredients of harmful bacteria, and can effectively inhibit the growth of carbon steel corrosion bacteria.
The plant-based composite bacteriostatic agent provided by the invention provides protection for the metal surface through an antiseptic mechanism and inhibits the growth of microorganisms through an antibacterial mechanism, so that an antibacterial composition with excellent and reliable corrosion inhibition effect is formed. The active ingredient in the plant extract is used as the main ingredient of the sustained release agent, and the bimetallic nanoparticles are used as the main ingredient of the sulfate reducing bacteria inhibitor, so that the prepared plant-based composite bacteriostatic agent has excellent corrosion inhibition and bacteriostasis performances. The plant-based composite bacteriostatic agent can effectively inhibit the growth of sulfate reducing bacteria and prevent the corrosion of carbon steel pipelines in oil fields through the combined synergistic effect of nano silver, nano copper and plant extracts. The example results show that the plant-based composite bacteriostatic agent provided by the invention can effectively reduce the growth activity of sulfate reducing bacteria and the weightlessness rate of carbon steel, reduce the corrosion of the sulfate reducing bacteria to the carbon steel, and can be applied to the anticorrosion operation of oilfield pipelines to be beneficial to the safe performance of oilfield production.
Further, the plant extract in the plant-based composite bacteriostat provided by the invention contains active substances with reducing power (such as gingerol or gingerol in gingerol), and can also reduce metal ions in a metal salt solution, so that the metal ions become zero-valent elemental metal, and the plant-based composite bacteriostat is obtained by reducing metal silver ions and metal copper ion solutions.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions of the prior art, the drawings that are needed in the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a FT-IR spectrum of ginger extract.
Fig. 2 is a photograph of the plant-based composite bacteriostatic agent prepared in examples 2 to 10.
FIG. 3 shows the results of laser particle sizer detection of bimetallic nanoparticles in the plant-based composite bacteriostat prepared in example 8.
FIG. 4 is an image of bimetallic nanoparticles at 200-800 nm wavelength of spectrophotometer in the plant based composite bacteriostat prepared in example 8.
FIG. 5-1 is an electron image of the X-ray energy spectrum of bimetallic nanoparticles in the plant-based composite bacteriostat prepared in example 8.
Fig. 5-2 shows the elemental composition of the bimetallic nanoparticles obtained by X-ray spectroscopy in the plant-based composite bacteriostat prepared in example 8.
FIGS. 5-3 are FT-IR images of the plant-based composite bacteriostat prepared in example 8.
FIG. 6 is a scanning electron microscope image of bimetallic nanoparticles in the plant-based composite bacteriostat prepared in example 8.
FIG. 7 is a scanning electron microscope image of the surface of the carbon steel treated with the plant-based composite bacteriostat prepared in example 8 and the carbon steel not treated with the plant-based composite bacteriostat after 15 days of corrosion by sulfate reducing bacteria.
FIG. 8 shows the formation of ferrous sulfide precipitates in SRB cultures after treatment with the plant based composite bacteriostat prepared in example 8 (left) and without the bacteriostat treatment (right), respectively, at 12.5. Mu.g/L.
FIG. 9 is a graph of corrosion rates of various treated carbon steels, wherein BNPs represent corrosion rates of carbon steels with the addition of 9 μg/mL of the plant based composite bacteriostat prepared in example 8; control represents the carbon steel corrosion rate profile without the addition of the plant-based composite bacteriostat.
FIG. 10 shows the results of stability test at 60℃of the plant-based composite antibacterial agent prepared in example 8.
FIG. 11 shows the adhesion of nano silver with different concentrations to corrosion products on the surface of the iron nail in comparative example 1.
Detailed Description
The invention provides a plant-based composite bacteriostatic agent for oil fields, which comprises bimetallic nanoparticles and plant extracts; the bimetal nanoparticle includes nano silver and nano copper.
In the present invention, the plant-based composite antibacterial agent is preferably obtained by mixing 80 to 150g of a plant extract prepared from a plant raw material with a metal precursor solution, more preferably 100g of a plant extract prepared from a plant raw material with a metal precursor solution. In the present invention, the metal precursor solution is composed of silver ions and copper ions; the extraction method of the plant extract is described in detail later, and is not described in detail herein. In the present invention, the molar concentration ratio of silver ions to copper ions in the metal precursor solution is preferably 0.25 to 0.75:0.25 to 0.75, more preferably 0.25:0.75, more preferably 0.25 to 0.75mmol/L of silver ions, 0.25 to 0.75mmol/L of copper ions, most preferably 0.25mmol/L of silver ions, and 0.75mmol/L of copper ions. The volume ratio of the metal precursor solution to the plant extract is 1-3: 1 to 3, more preferably 1 to 3:1, still more preferably 1 to 2:1, still more preferably 1:1. the preparation method of the plant-based composite bacteriostat prepared by adopting the metal precursor solution and the plant extract is described in detail below, and is not repeated here.
In the present invention, the bimetal nanoparticle is preferably in the form of an alloy, and the bimetal nanoparticle is preferably formed by combining zero-valent silver and copper at a nanoscale; the atomic ratio of nano silver to nano copper in each bimetallic nanoparticle is preferably 1:5-5:1, and more preferably 1: 2-2: 1, further preferably 1:1.5 to 1.5:1, more preferably 1:1, most preferably 7.45:7.29 or most preferably 4.35:5.15 or most preferably 5.34:1.67; the bimetallic nanoparticle is preferably diamond-shaped.
In the present invention, the particle diameter of the bimetal nanoparticle is preferably 20 to 120nm, more preferably 30 to 88nm, still more preferably 35 to 40nm, and most preferably 38nm. The bimetal nano particles are uniform in shape and small in granularity. In the invention, the particle size of the bimetal nano particles has remarkable influence on the effect of the plant-based composite bacteriostatic agent, and the smaller the nano particle size is, the larger the specific surface area is, and the better the catalytic capability in the bacteriostatic effect is; and large-particle-size nano particles injected into the stratum can block the stratum, so that an oil pipeline is blocked and the oil extraction effect is reduced.
The sources of the nano silver and the nano copper are not particularly limited, and the conventional products in the field can be adopted. In the present invention, the zero-valent silver and copper are mixed in the same particle, but the plant extract has biosurfactant, which can form repulsive force between small particles, and can not be continuously aggregated to form larger particles, but remain in a smaller nano-size.
In the invention, the bimetal nano particles are compounded by adopting two metal nano particles, and the geometry and the electronic structure of the nano simple substance particles can be adjusted by adding the two metal nano particles so as to improve the catalytic activity and the selectivity of the nano simple substance particles. The bimetal nano material has multi-metal characteristics in the aspects of size, shape, zeta potential, specific surface area and the like, is beneficial to the effective interaction with bacterial cell membranes, and further causes the destruction of a host immune system, active oxygen generation, protein dysfunction and DNA damage, so that the bimetal nano material can be used as an antibacterial active ingredient for harmful bacteria; on the other hand, the bimetallic nanoparticles have high surface energy and can catalyze the adsorption process of ginger extract on the surface of carbon steel. The nano silver and nano copper in the bimetal nano particles can play a synergistic technical effect in the aspects of resisting and inhibiting bacteria and relieving corrosion of oilfield steel pipes.
In the present invention, the plant extract preferably includes a reductive active material and a biosurfactant. In the present invention, the reducing active substance is preferably gingerol; the gingerol preferably comprises gingerol and/or gingerol; the biosurfactant is preferably a macromolecular active containing hydroxyl groups, more preferably a macromolecular active containing a large number of hydroxyl groups. In the present invention, the macromolecular active material containing a large number of hydroxyl groups is preferably a polysaccharide. In the invention, the biological surface active substances in the plant extract can form repulsive force among small particles, and can not be continuously aggregated to form larger particles, but keep the smaller nano-size, so that the bimetal nano-particles have the characteristics of uniform shape and smaller particle size in the plant extract.
In the present invention, the plant material is preferably ginger; the plant extract is preferably ginger extract, and contains a large amount of active ingredients such as gingerol, polysaccharide and the like. In the present invention, the plant extract is preferably a plant aqueous extract. The preparation method of the plant extract is not particularly limited, and the method is carried out by adopting a water extraction method of a plant raw material which is conventional in the field. Ethanol-based, which poses a threat to production safety and is costly, is not considered in the present invention.
In the present invention, the preparation method of the plant extract preferably includes, but is not limited to, the following steps: mixing plant raw materials with water for water extraction to obtain a primary water extract; and (3) defibrating the preliminary water extract to obtain a plant extract.
In the present invention, the plant material is preferably a fresh plant material free of diseases. The plant material is preferably washed and sliced before being mixed with water. The method for cleaning is not particularly limited, and the cleaning can be performed by adopting a conventional cleaning method. The washing mainly removes impurities on the plant material. The specification and method of the slicing are not particularly limited in the present invention, and the plant material is preferably sliced into 2.0mm slices by using the specification and method of slicing conventional in the art.
After obtaining the plant slice, the invention preferably carries out microwave treatment on the plant slice, wherein the power of the microwave treatment is preferably 2000-3000 MHz, more preferably 2450MHz; the time of the microwave treatment is preferably 4 to 6 minutes, more preferably 5 minutes. The invention can improve the extraction efficiency of active substances in plant raw materials by carrying out microwave treatment on plant slices. The microwave treatment device is not particularly limited, and a conventional microwave treatment device in the field can be adopted.
After the plant slice after microwave treatment is obtained, the plant slice after microwave treatment is mixed with water for water extraction. In the present invention, the water is preferably deionized water; the mass ratio of the plant slices after microwave treatment to the water is preferably 1:4-6, more preferably 1:5. The temperature of the water extraction is preferably 50-70 ℃, more preferably 60 ℃; the water extraction time is preferably 40 to 60 minutes, more preferably 50 minutes. The method for maintaining the temperature in the reaction system is not particularly limited, and a conventional temperature maintaining method in the art may be employed. In the present invention, the means for maintaining the temperature of the reaction system may be any one of a water bath, an incubator and an electric heating jacket, and more preferably a water bath.
After the primary water extract is obtained, the invention carries out defibration on the primary water extract to obtain the plant extract. In the present invention, the defibration method is preferably vacuum filtration. The method for vacuum filtration is not particularly limited, and the conventional vacuum filtration method in the field is adopted. After the vacuum filtration, the invention preferably carries out centrifugation on the filtrate obtained by the filtration, and the rotation speed of the centrifugation is preferably 8000 Xg; the centrifugation time is preferably not less than 5 minutes, more preferably 5 to 10 minutes, and still more preferably 5 minutes. The vacuum filtration and centrifugation operation of the invention mainly remove plant cellulose and insoluble substances such as broken cells, dust and the like in the extract.
After the preliminary extract is defibrated and impurity-removed, the invention preferably also comprises cooling and standing to obtain a plant extract; the cooling and standing time is preferably 24 hours. The cooling and standing purpose is to ensure that the metal precursor solution and the plant extract are in the same state at the beginning of the synthesis reaction, and can be heated from the same temperature without the occurrence of rapid aggregation and precipitation. In the present invention, the plant extract may be used as a reducing agent and a dispersing agent for bimetallic nanoparticles and as a plant-based carbon steel corrosion inhibitor. The plant extract contains active substances with reducing power (such as gingerol or gingerol in gingerol), and metal ions in a metal salt solution can be reduced when the plant-based composite antibacterial agent is prepared, so that the metal ions become zero-valent elemental metal. Meanwhile, macromolecular substances (such as polysaccharide and the like) containing a large amount of hydroxyl groups in the plant extract can prevent the aggregation process of metal nano particles before the metal particles are aggregated into particles with larger sizes, so that the process of uniformly dispersing the small-particle-size simple-substance metals is realized. Meanwhile, the plant extract contains polar groups which are extremely easy to protonate, such as hydroxyl, carbonyl, benzene ring and the like, and the protonated plant extract can be adsorbed on the surface of steel under the action of static electricity in an environment for relieving corrosion; meanwhile, oxygen atoms and iron atoms do not occupy empty d orbits to form coordination bonds so as to generate chemical adsorption, and a good adsorption film layer is formed on the surface of the carbon steel to slow down corrosion. The oxygen-containing polar group of polysaccharide substance in plant extract has a large number of lone pair electrons and can be combined with Fe in solution 2+ The chelate is adsorbed on the metal surface, and the corrosion inhibition effect is further enhanced under the catalysis of bimetallic nano-particles.
The invention also provides a preparation method of the plant-based composite bacteriostat, which comprises the following steps:
mixing a silver ion solution and a copper ion solution to obtain a metal precursor solution;
and mixing the metal precursor solution with the plant extract to obtain the plant-based composite bacteriostatic agent.
The invention mixes silver ion solution and copper ion solution to obtain metal precursor solution.
In the present invention, the molar concentration ratio of silver ions to copper ions in the metal precursor solution is preferably (0.25 to 0.75): (0.25 to 0.75), more preferably 0.25:0.75, more preferably 0.25 to 0.75mmol/L of silver ions, 0.25 to 0.75mmol/L of copper ions, most preferably 0.25mmol/L of silver ions, and 0.75mmol/L of copper ions. The source of silver ions in the invention is preferably silver nitrate; the source of copper ions is preferably copper sulfate. The sources of silver ions and copper ions are not particularly limited, and the conventional silver ion reagents and copper ion reagents in the field are adopted. The present invention is not particularly limited in the arrangement of the silver ion solution and the copper ion solution, and the solution arrangement method conventional in the art may be adopted. In the present invention, the metal precursor solution preferably cannot contain chloride ions, otherwise the plant extract has insufficient reducing power to displace the elemental metal particles. The molar concentration ratio of silver ions to copper ions in the metal precursor solution is favorable for reasonable configuration of the prepared nano silver simple substance and nano copper simple substance, so that nano silver and nano copper atoms in the bimetallic nanoparticle alloy in the prepared plant-based composite bacteriostatic agent exist in a form of about 1:1; meanwhile, the molar concentration ratio of silver ions to copper ions in the metal precursor solution is favorable for obtaining bimetallic nanoparticles with smaller particle sizes.
After the metal precursor solution is obtained, the metal precursor solution is mixed with the plant extract to obtain the plant-based composite bacteriostatic agent.
In the present invention, the volume ratio of the metal precursor solution to the plant extract is preferably 1 to 3:1 to 3, more preferably 1 to 3:1, still more preferably 1 to 2:1, and still more preferably 1:1. in the present invention, the ratio of the metal precursor solution to the plant extract is advantageous for obtaining the bimetal nanoparticle having a smaller particle diameter. The mode of mixing the metal precursor solution and the plant extract is preferably that the metal precursor solution is added into the plant extract; the metal precursor solution is preferably added to the plant extract with stirring; the stirring mode is preferably magnetic stirring. The stirring rate is not particularly limited, and the stirring is uniformly carried out by adopting the conventional stirring rate in the field. In the present invention, the metal precursor solution is mixed with the plant extract, and then the temperature in the reaction system is preferably maintained at 75 to 95 ℃, more preferably at 80 to 95 ℃, and still more preferably at 95 ℃; the temperature holding time is preferably 15 to 45 minutes, more preferably 30 minutes. The method for maintaining the temperature in the reaction system is not particularly limited, and a conventional temperature maintaining method in the art may be employed. In the present invention, the means for maintaining the temperature of the reaction system may be any one of a water bath, an incubator and an electric heating jacket, and more preferably a water bath. In the invention, the water bath process is the reduction and dispersion process of the bimetallic nanoparticles, and after the metal precursor solution is mixed with the plant extract, a certain temperature is maintained for a certain period of time, so that the active substances with reducing power in the plant extract (such as gingerol or gingerol in gingerol) are beneficial to reducing metal ions in the metal salt solution, so that the metal ions become zero-valent elemental metal particles. Meanwhile, macromolecular substances (such as polysaccharide and the like) containing a large number of hydroxyl groups in the plant extract can prevent the aggregation process of metal nano particles before the simple substance metal particles are aggregated into particles with larger sizes, so that the uniform dispersion process of the simple substance metals with small particle sizes is realized. In the present invention, the zero-valent silver and copper are mixed in the same particle during the reduction process, but due to the biosurfactant in the plant extract. This results in repulsive forces between the small particles that cannot continue to aggregate to form larger particles, while remaining at the smaller nano-size.
After the heat preservation is completed, the solution obtained after the metal precursor solution and the plant extract solution are mixed and reacted is preferably subjected to a standing treatment, wherein the standing treatment is preferably a dark treatment standing, and the time of the dark treatment standing is preferably 10-15 hours, more preferably 12 hours. In the invention, the dark treatment standing can enable the reduction reaction to be carried out more fully, reduce more particles and obtain a more stable plant-based composite bacteriostatic agent. After the standing treatment, the reaction liquid is preferably centrifuged, and the rotation speed of the centrifugation is preferably 4000 Xg; the time of the centrifugation is preferably 5 to 10 minutes, more preferably 5 minutes. The centrifugation mainly removes insoluble impurities in the solution after the reaction to obtain the plant-based composite bacteriostatic agent with a uniform and stable system.
The plant-based composite bacteriostatic agent prepared by the preparation method is a liquid preparation. In the invention, when the plant-based composite bacteriostat exists in a liquid preparation form, the existence form of the bimetallic nano-particles in the plant extract is fluid. The plant-based composite bacteriostat can also be a solid preparation. When the plant-based composite bacteriostat is a solid preparation, the invention preferably dries the liquid preparation of the plant-based composite bacteriostat to obtain the solid preparation; the drying mode is preferably vacuum freeze drying. When the plant-based composite bacteriostatic agent exists in a solid preparation, the plant-based composite bacteriostatic agent can be dispersed in water and is directly applied to the slow release of oilfield carbon steel; ultrasound is preferably performed during the dispersion.
The preparation method of the plant-based composite bacteriostat provided by the invention is a simple method for synthesizing the plant-based composite bacteriostat, and has the advantages of high corrosion inhibition rate, wide raw material sources, low cost and the like compared with the prior art. The bacteriostasis degree is in linear correlation with the concentration of the plant-based composite bacteriostat. The bimetallic nano particles in the plant-based composite bacteriostatic agent prepared by the preparation method have the advantages of uniform shape and smaller particle size, and have larger surface energy, so that the plant-based composite bacteriostatic agent is beneficial to catalytic bacteriostasis and corrosion inhibition activity. Because the bimetallic nano particles have larger specific surface area, the bimetallic nano particles can catalyze better adsorption capacity when being combined with plant extracts, and the metal nano particles have killing capacity to bacterial cells, thereby inhibiting the growth of harmful bacteria.
The invention also provides application of the plant-based composite bacteriostatic agent in bacteriostasis. In the invention, the plant-based composite bacteriostat can inhibit the growth of sulfate-reducing bacteria. The plant-based composite bacteriostat provided by the invention can inhibit the bacillus and/or vibrio desulphurisation, so that the bacillus and/or vibrio desulphurisation is prevented from pitting on the surface of carbon steel, and the generation of hydrogen sulfide gas and ferrous sulfide precipitation is avoided.
The invention also provides application of the plant-based composite bacteriostatic agent in corrosion inhibition of carbon steel. In the invention, the plant-based composite bacteriostatic agent can effectively inhibit the growth of sulfate reducing bacteria and relieve the corrosion of carbon steel. The carbon steel is preferably Q235 carbon steel.
The invention also provides application of the plant-based composite bacteriostatic agent in corrosion inhibition of oil field oil delivery pipelines. In the invention, the plant-based composite bacteriostatic agent can be used for preventing potential safety hazards such as hydrogen sulfide gas in the oilfield operation process while relieving the corrosion of the oilfield carbon steel pipeline. The plant-based composite bacteriostatic agent has the characteristics of uniform property and smaller particle size, and can effectively prevent large-particle-size nano particles from being injected into stratum to block stratum, so that the oil pipeline is blocked and the oil extraction effect is reduced when the plant-based composite bacteriostatic agent is applied to slow release of oil pipeline in oil fields. In the invention, the plant-based composite bacteriostat can be applied to extreme environmental conditions of oil fields; such extreme environments include, but are not limited to, high temperature conditions, temperatures above 60 ℃, even above 75 ℃; the plant-based composite bacteriostat has particularly good stability under the extreme environmental conditions of an oil field.
For further explanation of the present invention, the plant-based composite bacteriostat for oil field, the preparation method and application thereof provided by the present invention are described in detail below with reference to the accompanying drawings and examples, but they should not be construed as limiting the scope of the present invention.
Example 1
The preparation method of the ginger extract comprises the following steps:
selecting 100g of fresh ginger without diseases, cleaning, and then cutting into slices with the thickness of 2.0mm to obtain ginger slices;
microwave-treating rhizoma Zingiberis recens slices at 2450MHz for 5min, adding the rhizoma Zingiberis recens slices into water at a ratio of 1:5, and water-bathing the rhizoma Zingiberis recens slices water solution at 60deg.C for 50min to obtain rhizoma Zingiberis recens primary water extract;
vacuum filtering the primary water extract of the ginger, and taking filtrate obtained by suction filtering to obtain a crude extract of the ginger;
centrifuging the crude extract of rhizoma Zingiberis recens at 8000 Xg for 5min, cooling, and standing to obtain rhizoma Zingiberis recens extract.
Active ingredient detection in ginger extract:
and (3) carrying out vacuum freeze drying on the prepared ginger extract to obtain ginger extract powder. After the ginger extract powder is made into tablets, FTIR spectrum experiments are carried out.
The chemical composition of the ginger extract was examined using FTIR spectrometer at room temperature to determine the presence of metal ion reducing substances in the active substances in the ginger aqueous extract. At 4000-400cm -1 Within a range of 4cm -1 Is recorded in the infrared spectrum 32 times and marks the signal peaks. The detection results are shown in FIG. 1.
As can be seen from FIG. 1, 3416cm -1 Deformation vibration at-ch=ch- (trans), 2927cm -1 Telescopic vibration of-CH at 1628cm -1 Stretching vibration at C=O, 1565cm -1 The left and right absorption bands are vibration absorption bands of benzene ring molecular skeleton, 1385cm -1 ，870cm -1 ，775cm -1 Is 1,3,5 trisubstituted of benzene ring. It can be seen that the radical information in the FT-IR spectrum of ginger extract has a good correspondence with the chemical structures of gingerol and gingerol, reference [1 ]]～[2]。
Reference is made to:
[1]Zhang Y P,Wang X,Shen Y,et al.Preparation and characterization of bio-nanocomposites film of chitosan and montmorillonite incorporated with ginger essential oil and its application in chilled beef preservation[J].Antibiotics,2021,10(7):796.
[2] he Wentao A square crystal Liang Xiaolong, song Jiming A ginger extract has a corrosion inhibiting effect on Q235 steel in hydrochloric acid solution [ J ]. Anhui university of Industrial university (Nature science edition), 2022,39 (01): 15-20.
Examples 2 to 10
The preparation of the plant-based composite bacteriostat comprises the following steps:
preparing a metal precursor solution containing silver ions and copper ions in a certain molar concentration;
under the condition of magnetic stirring, adding the metal precursor solution into the ginger extract prepared in the example 1 according to a certain volume ratio, uniformly mixing, carrying out water bath on the mixed solution of the metal precursor solution and the ginger extract for a certain time under the water bath condition with a certain temperature, carrying out dark treatment and standing for 12h after the water bath is finished, and centrifuging at 4000 Xg to remove insoluble impurities, thereby obtaining the plant-based composite bacteriostatic agent. The specific parameters of examples 2 to 10 are detailed in Table 1.
The liquid preparation of the plant-based composite bacteriostat prepared in examples 2 to 10 is shown in fig. 2, wherein GE1, GE2, GE3, GE4, GE5, GE6, GE7, GE8 and GE9 sequentially correspond to the plant-based composite bacteriostat prepared in examples 2 to 10.
Wherein example 2 corresponds to GE1, example 3 corresponds to GE2, example 4 corresponds to GE3, example 5 corresponds to GE4, example 6 corresponds to GE5, example 7 corresponds to GE6, example 8 corresponds to GE7, example 9 corresponds to GE8, and example 10 corresponds to GE9.
Table 1 specific parameters for preparing plant-based Compound bacteriostats in examples 2 to 10
Note that: ag in Table 1 + :Cu 2+ (mmol/L) also represents the concentration of two metal ions in the metal precursor solution, e.g. 0.75:0.25 refers to Ag in the metal precursor solution + The concentration is 0.75mmol/L, cu 2+ The concentration was 0.25mmol/L.
As can be seen from fig. 2, the plant-based composite bacteriostat prepared in examples 2 to 10 has different colors, which are caused by different silver-copper ratios in particles, the silver nano color is reddish brown, the copper nano is yellowish green, and the two metals in the bimetallic particles have different ratios, which cause the difference of colors.
Example 11
The particle size of the bimetallic nanoparticles in the plant-based composite bacteriostat prepared in examples 2 to 10 was detected by using a laser particle sizer.
The detection method comprises the following steps:
1. the computer is firstly turned on, then the instrument power switch is turned on, and the preheating is performed for about half an hour, so that the output power of the laser is stable.
2. A clean cuvette is prepared, the surface of the cuvette is required to be cleaned by alcohol and the like, and then the cuvette is dried to ensure that the surface is free of foreign matters. Then injecting purified water into the cuvette, wherein the height of the water surface is about 2/3 of the height of the cuvette, and the surface of the water is required to cover the position of the laser beam on the cuvette by 5 mm.
3. Opening a cover plate of the sample chamber, placing a cuvette filled with purified water into a fixed groove of the sample chamber, then taking off a baffle in front of the detector, adjusting the position of the cuvette to enable light spots reflected to the detector to slightly deviate upwards, ensuring that the reflected light spots do not irradiate on a receiving surface of the detector, and then covering the cover plate.
4. Samples were added and the main program was run.
The particle diameters of the bimetallic nanoparticles in the plant-based composite bacteriostat prepared in examples 2 to 10 obtained by detection are shown in table 2. The detection result of the laser particle sizer of the plant-based composite bacteriostatic agent prepared in example 8 is shown in fig. 3.
Table 2 results of particle size detection of bimetallic nanoparticles in plant-based composite bacteriostat prepared in examples 2 to 10
| Examples | Group of | Average particle diameter(nm) |
| Example 2 | GE1 | 6284 |
| Example 3 | GE2 | 2886 |
| Example 4 | GE3 | 120 |
| Example 5 | GE4 | 1650 |
| Example 6 | GE5 | 88 |
| Example 7 | GE6 | 13690 |
| Example 8 | GE7 | 38 |
| Example 9 | GE8 | 712 |
| Example 10 | GE9 | 6375 |
As can be obtained from table 2, the degree of influence of different conditions on the particle size of the bimetallic nanoparticles in the plant-based composite bacteriostatic agent is different, wherein the degree of influence of different conditions on the particle size is as follows: temperature > metal ion concentration ratio > metal precursor to plant extract volume ratio > reaction time. Wherein, the particle size of the bimetallic nanoparticles in the plant-based nano-bacteriostat prepared in example 8 is the smallest. As can be seen from FIG. 3, the particle size of the bimetallic nanoparticles in the plant-based nano-bacteriostat prepared in example 8 is mostly concentrated in the range of 20-50 nm, and the particles with the particle size of 20-50 nm account for 89.94% of the total particles. Since agglomeration and growth readily occur after the metal ions are reduced to zero-valent metals, it is important to find suitable stabilizers to keep the particles at the nanoscale. The ginger extract used in the invention contains a large amount of macromolecular substances with hydroxyl groups, which is favorable for fully and uniformly dispersing the nanometer in a system. Particles with a size of 20-50 nm account for 89.94% of the total particle size, which indicates the uniformity and monodispersity of the bimetallic nanoparticles in the ginger extract system.
Example 12
The plant-based composite bacteriostatic agent prepared in example 8 was detected using a spectrophotometer. The detection method comprises the following steps:
1. zeroing the ultraviolet spectrophotometer with rhizoma Zingiberis recens extract;
2. the glass dish is rinsed three times by using the composite bacteriostat, and the absorbance at the wavelength of 200-800 nm is read. The detection results are shown in FIG. 4.
As can be taken from fig. 4, the ultraviolet visible spectrum of the bimetal nanoparticles in the plant-based composite antibacterial agent prepared in example 8 shows characteristic absorption peaks at 300nm, which demonstrates the generation of the bimetal nanoparticles. And the synthesized bimetal nanoparticles can be rapidly formed within 60 minutes. After the preparation of the plant-based composite bacteriostat is completed for 12 hours, absorbance detection is carried out again, and as a result, the maximum absorption peak of the plant-based composite bacteriostat is found to be unchanged, and no precipitation is generated by centrifugation. The plant-based composite bacteriostat is shown to remain stable after 12 hours of preparation. This is important for application of the composite bacteriostatic agent system in oil fields.
Example 12-2
The plant-based composite bacteriostats prepared in examples 2 to 7 and examples 9 to 10 were examined using a spectrophotometer. The detection method comprises the following steps:
1. Zeroing the ultraviolet spectrophotometer with rhizoma Zingiberis recens extract;
2. the glass dish is rinsed three times by using the composite bacteriostat, and the absorbance at the wavelength of 200-800 nm is read. The results of the detection were similar to FIG. 4, in that the peak widths obtained by the detection of examples 2 to 7 and examples 9 to 10 were larger. The ultraviolet visible spectrum of the bimetallic nanoparticles in the plant-based composite bacteriostat prepared in examples 2 to 7 and examples 9 to 10 showed characteristic absorption peaks at 300nm, which demonstrated the generation of bimetallic nanoparticles. And the synthesized bimetal nanoparticles can be rapidly formed within 60 minutes. The plant-based composite bacteriostat is stable after 12 hours from the completion of the preparation, and the plant-based composite bacteriostat is not precipitated after centrifugation and the ultraviolet characteristic absorption peak is not changed.
Example 13-1
1. The solid preparation of the plant-based composite bacteriostatic agent prepared in example 8 was detected using an X-ray spectrometer.
A very thin layer of gold is sprayed onto the surface of the sample by vapor deposition to ensure good conductivity of the sample. The EDX detector was connected to SEM instrument (Oxford instruments). Energy dispersive X-ray spectrometry was used to obtain the composition of the bi-metallic nanoparticles and elemental analysis to determine the elemental composition of the plant-based composite bacteriostat. The results of the detection are shown in FIG. 5-1, FIG. 5-2 and Table 3-1.
TABLE 3-1 elemental composition of plant-based Compound bacteriostat prepared in example 8
As can be seen from Table 3 and FIGS. 5-2, ag (26.11%) and Cu (16.52%) were present in the Ag/Cu bimetallic nanoparticles in the plant-based composite bacteriostatic agent system synthesized in example 8 of the present invention, and C, N, O was coated outside the Ag/Cu particles. It can be seen that the reducibility of ginger extract has the potential to synthesize bimetallic nanoparticles.
2. The solid preparation of the plant-based composite bacteriostatic agent prepared in example 8 was detected using an FT-IR spectrometer.
And (3) performing vacuum freeze drying on the plant-based composite bacteriostat prepared in the example 8 to obtain a plant-based composite bacteriostat solid preparation. And (3) carrying out FT-IR spectrum experiments after the solid preparation of the plant-based composite bacteriostat is prepared into tablets.
And detecting chemical components of the plant-based composite bacteriostatic agent solid preparation by using an FT-IR spectrometer at room temperature to determine active substances of the plant-based composite bacteriostatic agent. At 4000-400cm -1 Within a range of 4cm -1 Is recorded in the infrared spectrum 32 times and marks the signal peaks. The detection results are shown in FIGS. 5-3.
From FIGS. 5-3, 1628cm of synthesized nanoparticles were observed -1 And 1761cm -1 the-OH absorption peak at the position is reserved, and the macromolecular active substances rich in hydroxyl are of great significance for adsorbing the bacteriostat on the surface of the carbon steel.
Example 13-2
The solid formulations of the plant-based composite bacteriostat prepared in examples 2 to 7 and examples 9 to 10 were tested using an X-ray spectrometer. The elemental compositions of the plant-based composite bacteriostats prepared in examples 2 to 7 and examples 9 to 10 were determined as shown in Table 3-2.
TABLE 3-2 elemental composition of plant-based Compound bacteriostats prepared in examples 2 to 7 and examples 9 to 10
Note that: meaning that no relevant data is detected.
The electron images obtained by the X-ray spectrometer detection of the plant-based composite bacteriostat prepared in examples 2 to 7 and examples 9 to 10 are also similar to those of FIG. 5-1. As can be seen from Table 3-2, ag and Cu exist in the Ag/Cu bimetallic nanoparticles in the plant-based composite bacteriostatic agent system synthesized by the invention, and C, N, O is wrapped outside the Ag/Cu particles. The reducibility of ginger extract has proved to have the potential of synthesizing bimetallic nanoparticles.
Example 14
The surface morphology of the bimetallic nanoparticles in the plant-based composite bacteriostat prepared in example 8 was observed at an accelerating voltage of 15kV using a high resolution Zeiss Merlin Compact scanning electron microscope, with a magnification of 40kX. The surface morphology of the bimetallic nanoparticles in the plant-based composite bacteriostat prepared in example 8 is shown in fig. 6.
The morphology of the bimetallic nanoparticles was observed using a scanning electron microscope, as shown in fig. 6. The image shows that the bimetal nano particles are diamond-shaped, and the particle size is about 38 nm. The whole observation of the scanned image shows that the ginger extract can be used for synthesizing a bimetal nano system with uniform and stable dispersion shape through the reduced metal salt solution.
Example 14-2
The surface morphology of the bimetallic nanoparticles in the plant-based composite bacteriostats prepared in examples 2 to 7 and examples 9 to 10 was observed at an accelerating voltage of 15kV using a high resolution Zeiss Merlin Compact scanning electron microscope, with a magnification of 40k X.
The surface morphology of the bimetallic nanoparticles in the plant-based composite bacteriostat prepared in examples 2 to 7 and examples 9 to 10 was also similar to that of fig. 6, and the bimetallic nanoparticles were diamond-shaped, wherein the particle diameter of the bimetallic nanoparticles in the plant-based composite bacteriostat prepared in example 2 was about 6284nm, the particle diameter of the bimetallic nanoparticles in the plant-based composite bacteriostat prepared in example 3 was about 2886nm, the particle diameter of the bimetallic nanoparticles in the plant-based composite bacteriostat prepared in example 4 was about 120nm, the particle diameter of the bimetallic nanoparticles in the plant-based composite bacteriostat prepared in example 5 was about 1650nm, the particle diameter of the bimetallic nanoparticles in the plant-based composite bacteriostat prepared in example 6 was about 88nm, the particle diameter of the bimetallic nanoparticles in the plant-based composite bacteriostat prepared in example 7 was about 712nm, and the particle diameter of the bimetallic nanoparticles in example 9 was about 6375 nm.
Example 15
Detection of bacteriostatic effect of plant-based composite bacteriostatic agent prepared in example 8
Preparation of Postgate Medium
The sulfate reducing bacteria specific growth medium is a Postgate medium, and the Postgate medium comprises NaCl,5g/L; mgCl 2 ，1.8g/L；CaCl 2 ，0.02g/L；NH 4 Cl，0.3g/L；K 2 HPO 4 ，0.2g/L；KCl，0.5g/L；Na 2 SO 4 4g/L; sodium lactate, 1g/L; yeast extract, 1g/L; trace elements, 1mL/L;0.1% resazurin, 1mL/L; the vitamin complex solution is 2mL/L (pH 7.0).
The preparation of the Postgate culture medium is carried out according to the composition, and after the preparation of the culture medium is completed, an iron nail is placed so as to enable the sulfate reducing bacteria to grow in an attached mode. Introducing nitrogen gas into each bottle for more than 30min, removing oxygen, and sterilizing at 121deg.C for 20min.
2. Preparation of sulfate-reducing bacteria cultures
1mL of oilfield produced water was added to each 30mL of the LPostgate medium to enrich sulfate reducing bacteria and obtain a corrosion culture.
3. Expansion culture
The sulfate reducing bacteria separated from the oilfield produced water are transferred and passaged for more than 4 generations, and the growth period of each generation is about seven days. The culture condition is anaerobic culture at 30 ℃. Cultures were then subjected to the apodization dilution method counting according to industry standard SY/T0532-2012, the culture standardization in each flask was adjusted to 10 5 Standardized culture per mL And (5) cultivating.
4. Determination of minimum inhibitory concentration
The minimum concentration of the plant-based composite bacteriostatic agent system which completely inhibits the growth of SRB after anaerobic culture at 30 ℃ for 14 days is detected.
The solid preparation of the plant-based composite bacteriostatic agent prepared in the example 8 is dissolved in a Postgate culture medium for the specific growth of sulfate-reducing bacteria according to a certain proportion, and the concentration of the plant-based composite bacteriostatic agent in the Postgate culture medium is controlled to be 100 mug/mL.
Performing multiple ratio dilution on the obtained Postgate culture medium containing the plant-based composite bacteriostat in an anaerobic bottle to obtain Postgate culture medium with the concentration of 100 mug/mL of the plant-based composite bacteriostat respectively, wherein the Postgate culture medium is marked as T1; the Postgate culture medium with the concentration of the plant-based composite bacteriostat of 50 mug/mL is marked as T2; the Postgate culture medium with the concentration of the plant-based composite bacteriostat of 25 mug/mL is marked as T3; the Postgate culture medium with the concentration of the plant-based composite bacteriostat of 12.5 mug/mL is marked as T4; the Postgate culture medium with the concentration of the plant-based composite bacteriostat of 6.25 mug/mL is marked as T5; the Postgate culture medium with the concentration of the plant-based composite bacteriostat of 3.125 mug/mL is marked as T6; the Postgate culture medium with the concentration of the plant-based composite bacteriostat of 1.5625 mug/mL is marked as T7; postgate medium with a plant-based composite bacteriostat concentration of 0 μg/mL was designated T8.
Meanwhile, positive control groups D1-D8 which are not inoculated with bacteria in a culture medium and contain plant-based composite bacteriostats with different concentrations are respectively arranged, wherein the concentration of the plant-based composite bacteriostats in the D1 is 100 mug/mL, the concentration of the plant-based composite bacteriostats in the D2 is 50 mug/mL, the concentration of the plant-based composite bacteriostats in the D3 is 25 mug/mL, the concentration of the plant-based composite bacteriostats in the D4 is 12.5 mug/mL, the concentration of the plant-based composite bacteriostats in the D5 is 6.25 mug/mL, the concentration of the plant-based composite bacteriostats in the D6 is 3.12 mug/mL, and the concentration of the plant-based composite bacteriostats in the D7 is 1.56 mug/mL, and the concentration of the plant-based composite bacteriostats in the D8 is 0 mug/mL; a culture medium without bacteriostatic agent is arranged, and the culture medium contains a negative control group D9 of sulfate reducing bacteria, and the negative control group eliminates the influence of other factors on the bacteriostatic degree.
Wherein the culture medium in the culture bottles of the T1-T8 groups and the D1-D9 groups is 20 mL/bottle. Each set of experiments was performed in 3 replicates. The remaining experimental groups were inoculated with 2mL of standardized cultures per flask, except that groups D1-D8 were not inoculated.
After 3 days of incubation, the absorbance at 600nm was measured with an ultraviolet spectrophotometer and corrected by subtracting the background absorbance of the positive control, eliminating the effect of the color of the bacteriostatic agent and the culture medium on bacterial cell growth. The results of the minimum inhibitory concentration measurements are shown in Table 4.
Table 4 the minimum inhibitory test results of the plant-based composite bacteriostat prepared in example 8
As can be seen from table 4, the plant-based composite bacteriostat prepared by the present invention has dose dependency on inhibition of sulfate-reducing bacteria, and bacterial activity decreases with increase of bacteriostasis and concentration. The plant-based composite bacteriostatic agent with the concentration of more than 6.25 mug/mL can obviously inhibit the growth of sulfate reducing bacteria by more than 50 percent. Therefore, the lowest inhibition concentration of the composite nano bacteriostatic agent synthesized by the invention on sulfate reducing bacteria is 6.25 mug/mL, and bacterial cells are sensitive to the plant-based composite bacteriostatic agent at the concentration.
5. Carbon steel corrosion inhibition effect detection
And (3) taking the carbon steel soaked in the SRB culture, polishing the carbon steel step by step through 150-2000 mesh sand paper, and removing an oxide layer and uneven mechanical scratches on the surface of the carbon steel to obtain the carbon steel with smooth surface and no corrosion.
Postgate medium was prepared, and a piece of 1 cm. Times.1 cm. Times.0.2 cm of the carbon steel having a smooth surface and no corrosion was placed in each flask, and 30mL of the medium was contained in each flask. Introducing nitrogen gas into each bottle for more than 30min, removing oxygen, and sterilizing at 121deg.C for 20min.
Cultures of the plant-based complex bacteriostat Postgate medium prepared in example 8 were added to the above medium at 6.25 μg/mL, and were designated as experiment 1; cultures without the addition of the plant-based complex bacteriostat to the above medium were scored as experiment 2. Both sets of experiments were inoculated with 5mL of standardized cultures, respectively. Anaerobic cultivation is carried out for 15 days at the temperature of 30 ℃, corrosion products on the surface of the carbon steel are cleaned after cultivation is finished, and the surface change of the carbon steel is observed by using a scanning electron microscope, as shown in figure 7, wherein the left image is a carbon steel scanning electron microscope image which is not treated by a bacteriostat, and the right image is a carbon steel scanning electron microscope image which is treated by a plant-based composite bacteriostat.
From FIG. 7, it can be observed that the carbon steel surface in the culture without the bacteriostatic agent becomes very rough, there are many corrosion points, and the corrosion points are connected with each other to form larger corrosion pits due to the higher concentration of sulfate-reducing bacteria; and the carbon steel surface treated by adding 6.25 mug/mL of the composite nano bacteriostatic agent is relatively flat, and only a small amount of water and local corrosion trace caused by culture medium components are present.
6. Adhesion test
The inhibition of the sulfate reducing bacteria biofilm biomass by the plant-based composite bacteriostat prepared in example 8 was evaluated and quantified by a crystal violet test.
And (3) taking Q235 carbon steel soaked in SRB culture, polishing the carbon steel step by step through 150-2000 mesh sand paper, and removing an oxide layer and uneven mechanical scratches on the surface of the carbon steel to obtain the carbon steel with smooth surface and no corrosion.
Postgate medium was prepared by placing a piece of 1 cm. Times.1 cm. Times.0.2 cm Q235 carbon steel, smooth in surface and free of corrosion, in each flask, and 10mL of medium was placed in each flask. Introducing nitrogen gas into each bottle for more than 30min, removing oxygen, and sterilizing at 121deg.C for 20min.
8 sets of experiments were set up, each set of experiments being performed in a separate flask, each set of experiments being performed in 3 replicates. The components in the culture medium of the 8 groups of experiments are respectively Postgate culture medium containing 100 mug/mL plant-based composite bacteriostat; postgate medium containing 50 μg/mL plant-based complex bacteriostat; postgate medium containing 25 μg/mL plant-based composite bacteriostat; postgate medium containing 12.5 μg/mL plant-based complex bacteriostat; postgate medium containing 6.25 μg/mL plant-based complex bacteriostat; postgate medium containing 3.12 μg/mL plant-based composite bacteriostat; postgate medium containing 1.56 μg/mL plant-based complex bacteriostat; postgate medium containing 0 μg/mL plant-based complex bacteriostat. Meanwhile, the positive control group is set as sterile normal saline, and the culture medium without adding the plant-based composite bacteriostat and with standard inoculums and the negative control group are set as the culture medium with the plant-based composite bacteriostat with different concentrations corresponding to the test group respectively added, but without inoculating the standardized culture.
Except for the negative control group, 0.5mL of standardized cultures were inoculated in each of the above-mentioned remaining media.
After 7 days of incubation at 30℃the contents of the anaerobic flask were aspirated and rinsed twice with 10mL of sterile phosphate buffered saline (pH 7). The attached biofilm in each bottle was fixed with glutaraldehyde for 15 min, stained with crystal violet (1%, w/v) and oven dried at 50 ℃ for 1h. Excess stain was rinsed off in large amounts with distilled water. Finally, the adhered bacteria were dissolved with 33% glacial acetic acid. Absorbance at 490nm was measured in an ultraviolet spectrophotometer to quantify the amount of biofilm formed. The inhibition rate of biofilm formation was calculated as follows:
the inhibition rate of the formation of the biological film obtained by the experiment is shown in Table 5; the generation of ferrous sulfide precipitate in the bottle after the treatment of the plant-based composite bacteriostatic agent is shown in figure 8.
TABLE 5 inhibition of sulfate-reducing bacteria biofilm biomass by plant-based composite bacteriostat prepared in example 8
As shown in Table 5, the inhibition degree of the biofilm formation was about 37% when the concentration of the plant-based composite bacteriostatic agent (1.5625 to 12.5. Mu.g/mL) was low. But can effectively inhibit 65% of biological film formation with the increase of the concentration of the bacteriostatic agent to more than 50 mug/mL. This demonstrates that the low concentration of the bacteriostatic agent has no relationship with the dosage of the bacteriostatic agent for the adhesion activity of the sulfate-reducing bacteria, while the high concentration of the bacteriostatic agent can significantly reduce the adhesion activity of the sulfate-reducing bacteria on the surface of the common Q235 carbon steel. The generation of ferrous sulfide precipitate in the bottle after treatment with the composite bacteriostat is shown by figure 8.
7. Weight loss test
The corrosion rate of carbon steel after treatment with the plant-based composite bacteriostat prepared in example 8 was evaluated according to the standard NACE-MR-0175-ISO-15156-2015.
And (3) taking Q235 carbon steel soaked in SRB culture, polishing the carbon steel step by step through 150-2000 mesh sand paper, and removing an oxide layer and uneven mechanical scratches on the surface of the carbon steel to obtain the carbon steel with smooth surface and no corrosion.
Dividing the Q235 steel carbon steel into 1cm×1cm×0.2cm Q235 carbon steel hanging pieces, weighing (precision 0.1 mg) respectively, sealing edges with paraffin wax, and keeping double sides with exposed surface area of 1cm 2 Exposed area of 2cm 2 。
Postgate medium was prepared and a piece of Q235 carbon steel coupon was placed in each flask, each flask containing 10mL of medium. Introducing nitrogen gas into each bottle for more than 30min, removing oxygen, and sterilizing at 121deg.C for 20min.
4 sets of experiments were set up, each set of experiments was performed in separate flasks, each numbered record was made, and each set of experiments was performed in 4 replicates. The components in the culture medium of the 4 groups of experiments are respectively Postgate culture medium containing 0 mug/mL plant-based composite bacteriostat; postgate medium containing 3 μg/mL plant-based composite bacteriostat; postgate medium containing 6 μg/mL plant-based composite bacteriostat; postgate medium containing 9 μg/mL of plant-based complex bacteriostat. The 4 groups of experiments were inoculated with 0.5mL of standardized cultures, respectively.
Anaerobic culture at 30deg.C, and taking out hanging pieces from 4 groups of anaerobic culture bottles after 3 days, 6 days, 9 days, 12 days and 15 days. Hydrochloric acid pickling solution with urotropine content of 2% by mass (urotropine quality)The preparation method of the hydrochloric acid pickling solution with the weight percentage of 2 percent comprises the following steps: and adding urotropine into the hydrochloric acid solution, wherein the adding amount of the urotropine is 2% of the mass of the hydrochloric acid solution, the hydrochloric acid solution is hydrochloric acid solution with the volume percentage concentration of 12%), cleaning corrosion products on the surface of the hanging piece, flushing the surface of the sample piece with sterile deionized water, and packaging with filter paper. Drying in oven at 60deg.C to constant weight, cooling the sample to room temperature, and weighing again. The corrosion rate (g/m) was calculated as follows 2 ·h)：
Wherein: w (W) 0 Representing the original weight (g) of the coupon;
W i representing the final weight (g) of the coupon;
s represents the exposed surface area (m 2 )；
t is the etching time (h).
The corrosion rate of carbon steel is shown in Table 6; the weight loss of the plant-based composite bacteriostatic agent hanging tablet prepared in example 8 with the weight of 9 mug/mL is shown in table 6-1; a graph of carbon steel corrosion rates for the plant-based composite bacteriostat prepared in example 8 at 9 μg/mL is shown in FIG. 9.
TABLE 6 detection results of corrosion rates of carbon steel by plant-based composite bacteriostat prepared in example 8 at different concentrations
Table 6-1 9 μg/mL weight loss of plant-based composite bacteriostatic hanging tablet prepared in example 8
TABLE 6-2 Corrosion Rate Unit conversion coefficient
Note that: the density ρ of the Q235 carbon steel was 7.85.
Corrosion due to SRB is characterized as pitting and can be classified into four categories, light corrosion, moderate corrosion, severe corrosion and very severe corrosion according to international current standards for NACE. Wherein the corrosion rate is less than 0.127mm/a and is slight corrosion, and the corrosion rate is more than 0.308mm/a and is extremely serious corrosion. The change in corrosion rate of carbon steel at 30℃over 15 days was recorded in this example as shown in Table 6. The growth period of the group sulfate reducing bacteria without the composite bacteriostat added is started after the group sulfate reducing bacteria are cultured for 150 hours, and the corrosion rate is increased from the initial 0.101mm/a to 0.453mm/a, so that the group sulfate reducing bacteria become extremely severely corroded. While the carbon steel hanging piece of the group treated by the composite bacteriostatic agent keeps a slightly corroded state all the time in the experimental process of 15 days, and almost no weight change occurs.
8. Stability experiment of plant-based Compound bacteriostat prepared in example 8
200mL of Postgate culture medium is prepared at the temperature of 60 ℃, split charging is carried out on the culture medium into two 100mL anaerobic culture flasks, iron nails made of Q235 steel are respectively added, and the pipeline environment in the stratum is simulated. The culture medium containing iron nails (iron nails without rust) was sterilized at 121℃for 20min and then cooled to 60 ℃. 5mL of oilfield on-site SRB-containing water samples were inoculated into the bottles, respectively, and a bacteriostatic agent was added to one of the bottles at a concentration of 6.25. Mu.g/mL. After 15 days of incubation at 60 ℃, the changes in the flasks are shown in FIG. 10, where the left panel is the inoculated flask without bacteriostatic agent added and the right panel is the flask with bacteriostatic agent added at 6.25 μg/mL.
It can be seen from fig. 10 that severe SRB corrosion occurred in the bottle without the bacteriostatic agent, a large amount of ferrous sulfide precipitated, and the headspace gas had a taste of hydrogen sulfide. The SRB growth is basically inhibited in the culture added with the inhibitor, the culture in the bottle is not discolored, and the shape of the iron nail is complete.
Comparative example 1
Determination of minimum inhibitory concentration of nanosilver
The test method comprises the following steps: the Postgate culture medium is prepared, the final concentration of the nano silver Postgate culture medium prepared by a laboratory chemistry method is respectively 250 mug/mL, 125 mug/mL, 62.5 mug/mL, 31.25 mug/mL, 15.625 mug/mL, 7.8125 mug/mL and 0 mug/mL by a double dilution method, the nano silver-containing Postgate culture medium is respectively subpackaged into a penicillin bottle containing iron nails (the iron nails are rust-free) after sterilization, and then an injection needle is used for receiving oilfield produced water with a volume ratio of 5%, and anaerobic culture is carried out at 33 ℃ for one week. After the bottle is removed, taking out the iron nails to observe the adhesion condition of the corrosion products on the surfaces, wherein the corrosion condition of the iron nails is shown in figure 11, and the iron nails are the adhesion condition of the corrosion products on the surfaces of the iron nails after the oil field produced water is added to Postgate culture medium containing 0 mug/mL, 7.8125 mug/mL, 15.625 mug/mL, 31.25 mug/mL, 62.5 mug/mL, 125 mug/mL and 250 mug/mL nano silver in sequence from left to right.
From FIG. 11, it can be seen that the corrosion of the surface of the iron nail was relieved only when the concentration of the nano silver was 62.5. Mu.g/mL or more in the culture. The plant-based nano bacteriostatic agent is an order of magnitude higher than the plant-based composite bacteriostatic agent, so that the plant-based nano bacteriostatic agent can achieve better bacteriostatic effect and has less harm to the environment.
In conclusion, the plant-based composite bacteriostatic agent for the oil field can effectively inhibit the growth of sulfate reducing bacteria in the produced water of the oil field and reduce the adhesion of the sulfate reducing bacteria on the metal surface; and has a certain effect on relieving corrosion rate. The method is applied to relieving corrosion of sulfate reducing bacteria to oil pipelines, can effectively reduce corrosion rate, and has potential application prospect in pest antibacterial research in the fields of petroleum and natural gas. The plant extract and the bimetallic nanoparticles in the plant-based composite bacteriostat have the technical effect of synergistic effect in relieving carbon steel corrosion; the nano silver and nano copper in the bimetallic nano particles can also have the technical effect of synergistic interaction in the aspects of resisting bacteria and catalyzing corrosion inhibition of plant extract carbon steel.
Although the foregoing embodiments have been described in some, but not all, embodiments of the invention, it should be understood that other embodiments may be devised in accordance with the present embodiments without departing from the spirit and scope of the invention.
Claims (10)
1. The plant-based composite bacteriostatic agent for the oil field is characterized by comprising bimetallic nanoparticles and plant extracts; the bimetal nanoparticles comprise nano silver and nano copper;
the bimetal nanoparticle is formed by combining zero-valent silver and copper at a nanoscale; the atomic ratio of nano silver to nano copper in each bimetallic nanoparticle is 1:5-5:1;
the particle size of the bimetal nano particles is 20-50 nm;
the bimetal nano particles are diamond-shaped;
the plant extract is ginger extract;
the preparation method of the plant-based composite bacteriostat comprises the following steps:
mixing a silver ion solution and a copper ion solution to obtain a metal precursor solution;
mixing the metal precursor solution with a plant extract to obtain a plant-based composite bacteriostatic agent;
the molar concentration ratio of silver ions to copper ions in the metal precursor solution is (0.25-0.75): (0.25 to 0.75);
the volume ratio of the metal precursor solution to the plant extract is (1-3);
the metal precursor solution and the plant extract are mixed and then the temperature in the reaction system is kept at 75-95 ℃; the temperature maintaining time is 15-45 min;
the preparation method of the plant extract comprises the following steps:
Mixing plant raw materials with water for water extraction to obtain a primary water extract;
and (3) defibrating the preliminary water extract to obtain a plant extract.
2. The plant-based composite bacteriostat of claim 1, wherein the plant extract comprises a reducing active substance and a biosurfactant substance; the reducing active substance comprises gingerol; the biosurfactant includes macromolecular actives containing hydroxyl groups.
3. The plant-based composite bacteriostat of claim 1, wherein the atomic ratio of nano silver to nano copper in each bimetallic nanoparticle is 7.45:7.29, 4.35:5.15 or 5.34:1.67.
4. The plant-based composite bacteriostatic agent according to claim 1, wherein said bimetallic nanoparticles have a particle diameter of 38nm.
5. The plant-based composite bacteriostat according to claim 1, characterized in that the plant raw material is subjected to washing, slicing and microwave treatment before being mixed with water;
the power of the microwave treatment is 2000-3000 MHz; the microwave treatment time is 4-6 min.
6. The plant-based composite bacteriostat of claim 1, wherein the temperature of the water extraction is 50-70 ℃; the water extraction time is 40-60 min; the defibration method comprises vacuum filtration.
7. A method for preparing the plant-based composite bacteriostatic agent according to any one of claims 1 to 6, which is characterized by comprising the following steps:
mixing a silver ion solution and a copper ion solution to obtain a metal precursor solution;
mixing the metal precursor solution with a plant extract to obtain a plant-based composite bacteriostatic agent;
the molar concentration ratio of silver ions to copper ions in the metal precursor solution is (0.25-0.75): (0.25 to 0.75);
the volume ratio of the metal precursor solution to the plant extract is (1-3);
the metal precursor solution and the plant extract are mixed and then the temperature in the reaction system is kept at 75-95 ℃; the temperature maintaining time is 15-45 min.
8. The method according to claim 7, wherein the molar concentration of silver ions in the metal precursor solution is 0.25 to 0.75mmol/L and the molar concentration of copper ions is 0.25 to 0.75mmol/L.
9. The method according to claim 7, wherein the step of standing the reaction system after maintaining the temperature in the reaction system at 75 ℃ to 95 ℃; the standing is dark treatment standing; and standing for 10-15 h.
10. The use of a plant-based composite bacteriostat according to any one of claims 1 to 6 or a plant-based composite bacteriostat prepared by a preparation method according to any one of claims 7 to 9 in any one of (i) to (III),
Preparing a sulfate reducing bacteria inhibiting product;
(II) corrosion inhibition of carbon steel;
and (III) corrosion inhibition of oil field oil delivery pipelines.
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