CN115804374A - Sulfate reducing bacteria bactericide and application thereof - Google Patents

Sulfate reducing bacteria bactericide and application thereof Download PDF

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CN115804374A
CN115804374A CN202111073612.XA CN202111073612A CN115804374A CN 115804374 A CN115804374 A CN 115804374A CN 202111073612 A CN202111073612 A CN 202111073612A CN 115804374 A CN115804374 A CN 115804374A
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parts
bactericide
reducing bacteria
tank
water
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赵辉
杜勇
孟庆标
赵晓东
张�杰
李�权
洪继广
陈吉红
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China Petroleum And Chemical Corp Shengli Youtian Branch Zhuangxi Oil Rec Overy Fac
China Petroleum and Chemical Corp
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China Petroleum And Chemical Corp Shengli Youtian Branch Zhuangxi Oil Rec Overy Fac
China Petroleum and Chemical Corp
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Abstract

The invention belongs to the technical field of petroleum engineering sewage treatment, and particularly relates to a sulfate reducing bacteria bactericide and application thereof. The bactericide comprises the following components in parts by weight: 10-40 parts of dodecyl dimethyl benzyl ammonium chloride, 0-20 parts of glutaraldehyde, 10-30 parts of A bactericide and 10-80 parts of water; the A bactericide is any one of alkyl diquaternary ammonium salt, dodecyl guanidine hydrochloride and hydroxypropyl gemini quaternary ammonium salt modified guanidine. The sulfate reducing bacteria bactericide disclosed by the invention is simple in composition, and has a remarkable sterilizing effect on sulfate reducing bacteria, especially alkali-resistant and variant sulfate reducing bacteria.

Description

Sulfate reducing bacteria bactericide and application thereof
Technical Field
The invention belongs to the technical field of petroleum engineering sewage treatment, and particularly relates to a sulfate reducing bacteria bactericide and application thereof.
Background
In oil field sewage and water injection systems, a large number of Sulfate Reducing Bacteria (SRB) exist, which reduce sulfate radicals to sulfur ions to propagate in large quantities, resulting in corrosion damage to surface facilities and underground pipelines and sulfide pollution, causing huge economic losses to oil fields.
Methods of inhibiting SRB include physical, chemical and biological methods. The physical method comprises the following steps: treatment with ionizing radiation, ultrasound or reflected radiation; changing medium environment, adjusting the pH value of the medium, and stopping the growth of the SRB when the pH value is lower than 4; injecting high salinity water or saline water, and reducing water content in the cell by osmotic pressure to inhibit SRB growth; hot water is periodically injected, etc. The biological method can prevent the corrosion of the microorganisms to the metal by utilizing the symbiosis, competition and antagonism relationship among the microorganisms. The chemical method mainly inhibits the reproduction of SRB by adding bactericide. The types of bactericides commonly used at present comprise quaternary ammonium salts and compound products; aldehyde fungicides, such as glutaraldehyde, acrolein; sulfur-containing compounds and compounds, such as dithiocyanomethane, isothiazolinone; oxidizing bactericides such as triclosan and the like; others are quaternary phosphonium salts.
Chinese patent application CN107488166A discloses a bactericide for sulfate reducing bacteria in oilfield sewage, which is prepared by reacting 1-propanol and 2,2,6-trimethyl-4-1,3-dioxycyclohexene-4-ketone to generate an intermediate, and then splitting by adopting a chiral reagent to obtain the final bactericide. The sterilizing rate of the bactericide on sulfate reducing bacteria in the oilfield sewage reaches more than 98 percent.
Chinese patent application CN102669103A discloses a bactericide for killing sulfate reducing bacteria, wherein the weight percentage of each component is as follows: industrial formaldehyde: 22.5% -25.0%; medical metronidazole: 2.5% -3.5%; industrial glutaraldehyde: 20.0% -25.05; water: and (4) the balance. The formaldehyde has strong toxicity, and the large amount of the bactericide can cause potential threat to the health of field workers.
The Chinese invention patent CN105145631B discloses an oil storage tank sulfate reducing bacteria inhibitor, which comprises the following components in parts by mass: 60-100 parts of glutaraldehyde or acrolein and/or 30-70 parts of dodecyl dimethyl benzyl ammonium bromide or dodecyl dimethyl benzyl ammonium chloride; 15-20 parts of lysozyme and 20-30 parts of protease; 10-20 parts of di-o-phenylenediaminyl acetate and/or 10-20 parts of ethylenediamine disuccinate; 5-10 parts of tetrakis hydroxymethyl phosphonium sulfate. The inhibitor contains lysozyme and protease, and has high production cost.
At present, with the long-term application of a sewage softening and fine water treatment system, the applicant continuously discovers that water output by the system also contains a large amount of sulfate reducing bacteria, and the applicant firstly discovers that the sulfate reducing bacteria exceed the standard and the flora are different and varied in the alkaline environment with the high pH value of pH = 10-11 by detecting the sulfate reducing bacteria, the pH value, the oxygen content, sulfides and the like of a production node of the sewage softening and fine water treatment system, collecting microorganism samples, carrying out enrichment culture, separating and optimizing strains, carrying out gene sequencing, comparing and analyzing and the like. For sulfate-reducing bacteria with stronger alkali resistance and drug resistance, a more effective bactericide is urgently needed.
SRB remains excessive by increasing the frequency of cleaning the system and adding conventional disinfectants prior to delivery. Therefore, there is a need for a bactericide effective in inhibiting post-mutation sulfate-reducing bacteria.
Disclosure of Invention
The invention mainly aims to provide a sulfate reducing bacteria bactericide. The sulfate reducing bacteria bactericide disclosed by the invention can effectively inhibit sulfate reducing bacteria, particularly has a strong inhibition effect on variation sulfate reducing bacteria with strong alkali resistance and drug resistance, and solves the problems that the variation sulfate reducing bacteria, the alkali resistance and the drug resistance are enhanced in the softening treatment process of oilfield sewage, and the prior art is difficult to inhibit the variation sulfate reducing bacteria.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention firstly provides a sulfate reducing bacteria bactericide, which comprises the following components in parts by weight: 10-40 parts of dodecyl dimethyl benzyl ammonium chloride, 0-20 parts of glutaraldehyde, 10-30 parts of A bactericide and 10-80 parts of water; the A bactericide is any one of alkyl diquaternary ammonium salt, dodecyl guanidine hydrochloride and hydroxypropyl gemini quaternary ammonium salt modified guanidine.
Further, the bactericide comprises the following components in parts by weight: 10-30 parts of dodecyl dimethyl benzyl ammonium chloride, 10-20 parts of alkyl bis-quaternary ammonium salt and 50-80 parts of water. The bactericide is named as SH-1 type bactericide.
Further, the alkyl bis-quaternary ammonium salt has 10 to 18 carbon atoms in alkyl group.
Further, the bactericide comprises the following components in parts by weight: 10-20 parts of dodecyl dimethyl benzyl ammonium chloride, 10-20 parts of dodecyl guanidine hydrochloride, 4-15 parts of glutaraldehyde and 45-76 parts of water. The bactericide is named as SH-2 type bactericide.
Further, the bactericide comprises the following components in parts by weight: 10-20 parts of dodecyl dimethyl benzyl ammonium chloride, 10-20 parts of hydroxypropyl gemini quaternary ammonium salt modified guanidine, 4-20 parts of glutaraldehyde and 40-76 parts of water. The bactericide is named as SH-3 type bactericide.
Furthermore, the number of the alkyl carbon atoms in the hydroxypropyl gemini quaternary ammonium salt modified guanidine is 10-18.
The invention also provides application of the sulfate reducing bacteria bactericide in softening treatment of oilfield sewage.
Compared with the prior art, the invention has the following technical advantages:
the sulfate reducing bacteria bactericide disclosed by the invention is simple in composition, and has a remarkable sterilizing effect on sulfate reducing bacteria, especially on alkali-resistant and variant sulfate reducing bacteria. Only a small amount of the bactericide of the invention needs to be added in the process of softening the oil field sewage, and the treated water contains less than or equal to 25 sulfate reducing bacteria per mL, thus reaching A-level water quality; the treated water is reinjected into the stratum, so that the damage to the stratum can be greatly reduced, and the antibacterial, anti-caking and anti-corrosion effects are obvious.
Drawings
FIG. 1 is a diagram illustrating the process of softening sewage according to the present invention;
FIG. 2 is a histogram of portal horizontal species distribution;
FIG. 3 is a diagram of the generic horizontal community Heatmap;
FIG. 4 is a chart of chao indices;
FIG. 5 is an ace index diagram;
FIG. 6 is a shannon index diagram;
FIG. 7 is a simpson index plot;
FIG. 8 is a weighted unifrac heat map;
FIG. 9 is a unweighted unifrac heat map;
FIG. 10 is a PCoA based on weighted unifrac;
FIG. 11 is a unweighted unifrac-based PCoA;
FIG. 12 is a unweighted unifrac tree diagram;
FIG. 13 is a unweighted unifrac tree diagram;
FIG. 14 is a weighted unifrc-based NMDS;
FIG. 15 is a unweighted unifrac-based NMDS;
FIG. 16 is a gate-level discrepancy matrix heat map;
FIG. 17 is a graph of a combination of species level sample clustering tree and histogram analysis.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of the stated features, steps, operations, and/or combinations thereof, unless the context clearly indicates otherwise.
In order to make the technical solutions of the present invention more clearly understood by those skilled in the art, the technical solutions of the present invention will be described in detail below with reference to specific embodiments.
Example 1
A sulfate reducing bacteria bactericide comprises the following components in parts by weight: 10 parts of dodecyl dimethyl benzyl ammonium chloride, 10 parts of dodecyl guanidine hydrochloride, 4 parts of glutaraldehyde and 76 parts of water.
The application of the sulfate-reducing bacteria bactericide in the oil field sewage softening treatment process, as shown in figure 1, specifically comprises the following steps:
step 1, when oil field sewage enters a softening tank for softening treatment, firstly, adjusting the pH value of an aqueous solution in the softening tank to 10.6, and then adding a flocculating agent for sedimentation to obtain low-hardness softened water;
step 2, when the low-hardness softened water enters the acid-base neutralization tank, adjusting the pH value of the aqueous solution in the acid-base neutralization tank to 9.0; after passing through a multi-media filter, adding 50mg/L of the bactericide in the embodiment 1, then filtering by a metal film filter, and conveying to a water injection tank;
step 3, discharging the deposited mud discharged from the softening tank to a mud sedimentation tank, conveying the deposited mud to a mud press, performing solid-liquid separation to form mud cakes, and transporting the mud cakes outwards;
and 4, discharging clear water at the upper part of the mud settling tank into a clear water tank for recycling.
Example 2
A sulfate reducing bacteria bactericide is composed of the following components in parts by weight: 13 parts of dodecyl dimethyl benzyl ammonium chloride, 14 parts of dodecyl guanidine hydrochloride, 5 parts of glutaraldehyde and 68 parts of water.
The application of the sulfate reducing bacteria bactericide in the softening treatment process of the oilfield sewage comprises the following steps:
step 1, when oil field sewage enters a softening tank for softening treatment, firstly, adjusting the pH value of an aqueous solution in the softening tank to 10.8, and then adding a flocculating agent for sedimentation to obtain low-hardness softened water;
step 2, when the low-hardness softened water enters the acid-base neutralization tank, adjusting the pH value of the aqueous solution in the acid-base neutralization tank to 8.9; after passing through a multi-media filter, 55mg/L of the bactericide in the embodiment 2 is added, and then the metal membrane filter is used for filtering, and the mixture is conveyed to a water injection tank;
step 3, discharging the deposited mud discharged from the softening tank to a mud sedimentation tank, conveying the deposited mud to a mud press, performing solid-liquid separation to form mud cakes, and transporting the mud cakes outwards;
and 4, discharging clear water at the upper part of the mud settling tank into a clear water tank for recycling.
Example 3
A sulfate reducing bacteria bactericide comprises the following components in parts by weight: 20 parts of dodecyl dimethyl benzyl ammonium chloride, 20 parts of dodecyl guanidine hydrochloride, 15 parts of glutaraldehyde and 55 parts of water.
The application of the sulfate reducing bacteria bactericide in the softening treatment process of the oilfield sewage comprises the following steps:
step 1, when oil field sewage enters a softening tank for softening treatment, firstly, adjusting the pH value of an aqueous solution in the softening tank to 11, and then adding a flocculating agent for sedimentation to obtain low-hardness softened water;
step 2, when the low-hardness softened water enters the acid-base neutralization tank, adjusting the pH value of the aqueous solution in the acid-base neutralization tank to 9.0; after passing through a multi-media filter, adding 50mg/L of the bactericide in the embodiment 3, then filtering by a metal film filter, and conveying to a water injection tank;
step 3, discharging the deposited sludge discharged by the softening tank to a sludge settling tank, conveying the sludge to a sludge press, performing solid-liquid separation to form a sludge cake, and then transporting the sludge cake;
and 4, discharging clear water at the upper part of the mud settling tank into a clear water tank for recycling.
Example 4
A sulfate reducing bacteria bactericide comprises the following components in parts by weight: 10 parts of dodecyl dimethyl benzyl ammonium chloride, 10 parts of dodecyl bis-quaternary ammonium salt and 80 parts of water.
The application of the sulfate reducing bacteria bactericide in the softening treatment process of the oilfield sewage comprises the following steps:
step 1, when oil field sewage enters a softening tank for softening treatment, firstly, adjusting the pH value of an aqueous solution in the softening tank to 10.7, and then adding a flocculating agent for sedimentation to obtain low-hardness softened water;
step 2, when the low-hardness softened water enters the acid-base neutralization tank, adjusting the pH value of the aqueous solution in the acid-base neutralization tank to 8.8; after passing through a multi-media filter, 48mg/L of the bactericide in the embodiment 4 is added, and then the metal membrane filter is used for filtering, and the mixture is conveyed to a water injection tank;
step 3, discharging the deposited mud discharged from the softening tank to a mud sedimentation tank, conveying the deposited mud to a mud press, performing solid-liquid separation to form mud cakes, and transporting the mud cakes outwards;
and 4, discharging clear water at the upper part of the mud settling tank into a clear water tank for recycling.
Example 5
A sulfate reducing bacteria bactericide comprises the following components in parts by weight: 30 parts of dodecyl dimethyl benzyl ammonium chloride, 20 parts of octadecyl bis-quaternary ammonium salt and 50 parts of water.
The application of the sulfate reducing bacteria bactericide in the softening treatment process of the oilfield sewage comprises the following steps:
step 1, when oil field sewage enters a softening tank for softening treatment, firstly, adjusting the pH value of an aqueous solution in the softening tank to 10.9, and then adding a flocculating agent for sedimentation to obtain low-hardness softened water;
step 2, when the low-hardness softened water enters the acid-base neutralization tank, adjusting the pH value of an aqueous solution in the acid-base neutralization tank to 8.9; after passing through a multi-media filter, adding 50mg/L of the bactericide in the embodiment 5, then filtering by a metal film filter, and conveying to a water injection tank;
step 3, discharging the deposited mud discharged from the softening tank to a mud sedimentation tank, conveying the deposited mud to a mud press, performing solid-liquid separation to form mud cakes, and transporting the mud cakes outwards;
and 4, discharging clear water at the upper part of the mud settling tank into a clear water tank for recycling.
Example 6
A sulfate reducing bacteria bactericide comprises the following components in parts by weight: 12 parts of dodecyl dimethyl benzyl ammonium chloride, 15 parts of dodecyl bis-quaternary ammonium salt and 73 parts of water.
The application of the sulfate reducing bacteria bactericide in the softening treatment process of the oilfield sewage comprises the following steps:
step 1, when oil field sewage enters a softening tank for softening treatment, firstly, adjusting the pH value of an aqueous solution in the softening tank to 10.7, and then adding a flocculating agent for sedimentation to obtain low-hardness softened water;
step 2, when the low-hardness softened water enters the acid-base neutralization tank, adjusting the pH value of the aqueous solution in the acid-base neutralization tank to 8.9; after the mixture passes through a multi-media filter, 46mg/L of the bactericide in the embodiment 6 is added, and then the mixture is filtered by a metal film filter and is conveyed to a water injection tank;
step 3, discharging the deposited mud discharged from the softening tank to a mud sedimentation tank, conveying the deposited mud to a mud press, performing solid-liquid separation to form mud cakes, and transporting the mud cakes outwards;
and 4, discharging clear water at the upper part of the mud settling tank into a clear water tank for recycling.
Example 7
A sulfate reducing bacteria bactericide comprises the following components in parts by weight: 10 parts of dodecyl dimethyl benzyl ammonium chloride, 10 parts of hydroxypropyl gemini quaternary ammonium salt modified guanidine, 4 parts of glutaraldehyde and 76 parts of water.
The application of the sulfate reducing bacteria bactericide in the softening treatment process of the oilfield sewage comprises the following steps:
step 1, when oil field sewage enters a softening tank for softening treatment, firstly, adjusting the pH value of an aqueous solution in the softening tank to 11.1, and then, adding a flocculating agent for sedimentation to obtain low-hardness softened water;
step 2, when the low-hardness softened water enters the acid-base neutralization tank, adjusting the pH value of the aqueous solution in the acid-base neutralization tank to 9.0; after passing through a multi-media filter, adding 52mg/L of the bactericide described in the embodiment 7, then filtering by using a metal film filter, and conveying to a water injection tank;
step 3, discharging the deposited mud discharged from the softening tank to a mud sedimentation tank, conveying the deposited mud to a mud press, performing solid-liquid separation to form mud cakes, and transporting the mud cakes outwards;
and 4, discharging clear water at the upper part of the mud settling tank into a clear water tank for recycling.
Example 8
A sulfate reducing bacteria bactericide comprises the following components in parts by weight: 13 parts of dodecyl dimethyl benzyl ammonium chloride, 14 parts of hydroxypropyl gemini quaternary ammonium salt modified guanidine, 15 parts of glutaraldehyde and 68 parts of water.
The application of the sulfate reducing bacteria bactericide in the softening treatment process of the oilfield sewage comprises the following steps:
step 1, when oil field sewage enters a softening tank for softening treatment, firstly, adjusting the pH value of an aqueous solution in the softening tank to 10.8, and then adding a flocculating agent for sedimentation to obtain low-hardness softened water;
step 2, when the low-hardness softened water enters the acid-base neutralization tank, adjusting the pH value of the aqueous solution in the acid-base neutralization tank to 8.8; after passing through a multi-media filter, 55mg/L of the bactericide in the embodiment 8 is added, and then the metal membrane filter is used for filtering, and the mixture is conveyed to a water injection tank;
step 3, discharging the deposited mud discharged from the softening tank to a mud sedimentation tank, conveying the deposited mud to a mud press, performing solid-liquid separation to form mud cakes, and transporting the mud cakes outwards;
and 4, discharging clear water at the upper part of the mud settling tank into a clear water tank for recycling.
Example 9
A sulfate reducing bacteria bactericide comprises the following components in parts by weight: 20 parts of dodecyl dimethyl benzyl ammonium chloride, 20 parts of hydroxypropyl gemini quaternary ammonium salt modified guanidine, 20 parts of glutaraldehyde and 40 parts of water.
The application of the sulfate reducing bacteria bactericide in the softening treatment process of the oilfield sewage comprises the following steps:
step 1, when oil field sewage enters a softening tank for softening treatment, firstly, adjusting the pH value of an aqueous solution in the softening tank to 10.9, and then adding a flocculating agent for sedimentation to obtain low-hardness softened water;
step 2, when the low-hardness softened water enters the acid-base neutralization tank, adjusting the pH value of the aqueous solution in the acid-base neutralization tank to 9.0; after passing through a multi-media filter, adding 52mg/L of the bactericide described in the embodiment 9, then filtering by using a metal film filter, and conveying to a water injection tank;
step 3, discharging the deposited sludge discharged by the softening tank to a sludge settling tank, conveying the sludge to a sludge press, performing solid-liquid separation to form a sludge cake, and then transporting the sludge cake;
and 4, discharging clear water at the upper part of the mud settling tank into a clear water tank for recycling.
(I) detecting sulfate reducing bacteria at each node in the process of treating softened water
In the normal operation state of the pile 74 station, sampling and detecting for 5 days from 2019.9.15-9.19 on site along the way, and detecting indexes such as SRB, pH, sulfide, dissolved oxygen and the like of each node, wherein experimental data are shown in tables 1 and 2.
Table 1 pile 74 station on-way sewage SRB bacteria detection table
Figure RE-GDA0003467824740000101
Figure RE-GDA0003467824740000111
Table 2 pile 74 station on-way sewage detection table
Figure RE-GDA0003467824740000112
Figure RE-GDA0003467824740000121
(1) The pH value of the incoming water is about 7, the SRB range is 6-250/ml, and the engineering design pH value is controlled to be about 10.0-10.5 so as to control the survival and growth of SRB bacteria. The detection data shows that the pH value of the outlet of the softening tank after softening by adding alkali is about 10.20, and the SRB range is 2.5 multiplied by 10 2 ~2.5×10 4 Number of pieces/ml combined with SRB of mud discharging port of 2.5 multiplied by 10 4 ~2.5×10 5 The number per ml is preliminarily deduced that the sludge at the bottom of the softening tank has the phenomena of bacterial breeding, propagation and variation;
(2) The pH value of the neutralization tank is adjusted to 9.0 by hydrochloric acid, the SRB value is 6 multiplied by 10 2 ~2.5×10 4 Each/ml, the bacteria in the softer tank slightly increase;
(3) The pH value of the carborundum filter tank is 9.0, the SRB value is 2.5 multiplied by 10 3 ~2.5×10 4 Each/ml is increased by one order of magnitude compared with the outlet of the neutralization tank, and the SRB value in backwashing water of the emery filter tank is 6 multiplied by 10 in combination with 2 ~ 2.5×10 4 The quantity per ml can preliminarily conclude that the intercepted precipitated particles cannot be completely flushed clean, and the carborundum filter material is possibly polluted;
(4) The pH value of the outlet of the metal membrane filter tank is 9.00, the SRB value is 2.5 multiplied by 10 2 ~2.5×10 3 The volume per ml is reduced by an order of magnitude compared with that of a carborundum filter tank, and the metal film filter tank has a certain interception effect.
(5) The sewage in the sewage tank comes from the upper part of the sludge tank, and the SRB value is 2.5 multiplied by 10 3 ~2.3×10 3 Per ml, and a mud discharge port (2.5X 10) 4 ~2.5×10 5 Pieces/ml) was reduced by one order of magnitude in relation to the open aeration of the sludge basin.
(6) Backwashing the buffer tank and sewage in the sewage pool into a softening recovery tank (the sewage in the sewage pool is pumped into the softening recovery tank for 24 hours, the backwashing is carried out once for 12 hours, and the sewage is pumped into the softening recovery tank after the buffer tank is settled for a period of time), the SRB value is 2.5 multiplied by 10 2 ~2.5×10 3 One per ml.
In summary, the SRB bacteria superstandard node is: softening tank sewage, a carborundum filter material and backwashing water quality; the carborundum filter material has the possibility of being polluted, secondary pollution can be caused when sewage passes through the carborundum filter material, the back washing effect is not obvious, and the carborundum filter material needs to be cleaned regularly. The SRB bacteria are not effectively inhibited at the pH value of about 10.2 of the softening tank, an indoor pH adjustment experiment needs to be carried out on incoming water, interference of other factors on the site is eliminated, and the influence of the pH on the SRB is separately inspected.
(II) investigating the influence of pH on SRB bacteria
The results of examining the pH values of the water supplied from the sewage system of the 74-stage pile and the SRB bacteria discharged from the softening tank by adjusting the water to different pH values with 30% NaOH are shown in tables 3 and 4, respectively.
TABLE 3 experiment of adjusting pH value of 74-station incoming water
Figure RE-GDA0003467824740000131
Table 4 experiment for adjusting pH of effluent from 74-station softening tank
Figure RE-GDA0003467824740000132
Figure RE-GDA0003467824740000141
As can be seen from tables 3 and 4, for the water coming from the pile 74 station, the indoor pH value adjustment has a relatively obvious inhibition effect on SRB bacteria, and the SRB content is 25/mL when the pH value is 9; however, the pH value of the effluent of the softening tank does not play a role in inhibiting SRB, which shows that the adaptability of bacteria in the water of the softening tank to high pH value is enhanced under the dynamic environment of continuously supplementing new water, and the effect of the conventional bactericide on SRB bacteria needs to be further examined.
(III) investigating the Effect of the Bactericide on the SRB bacteria
Taking the effluent of the softening tank on the spot, screening the bactericide indoors, taking different types of bactericides at the temperature of 40 ℃ on the spot, selecting different adding concentrations, and inspecting the sterilizing effect of the bactericides on SRB bacteria in the effluent of the softening tank to determine the proper adding concentration. The test results are shown in Table 5.
TABLE 5 screening evaluation of fungicides
Figure RE-GDA0003467824740000142
Figure RE-GDA0003467824740000151
The SRB content of the effluent of the softening tank is 6 multiplied by 10 2 The quantity per mL, the sterilizing effect of the on-site bactericide on the effluent of the softening tank in the detection concentration range is not good, and the conventional SJ bactericide has no effect on the on-site bactericide. Considering that the flora is likely to generate evolutionary variation, the strain needs to be isolated and identified in the next step.
(IV) microbial flora isolation and colony diversity analysis
The pile 74 is taken along the way of water sample and mud sample, the strain separation is carried out on the samples, and the microbial community difference among the samples is inspected.
TABLE 6 microbial community analysis sample name and number
Sample numbering Sampling site
1# Water outlet of filter
2# Pile 74 for supplying water
3# Pile 74 softened tank water outlet
4# Pile 74 sewage recovery tank effluent
1# mud sample: softening tank center cylinder
2# mud sample: mud bottom
(1) Histogram of colony structure composition
According to the result of the taxonomic analysis, the taxonomic comparison condition of one or more samples at each classification level can be known. In the results, two pieces of information are contained: what microorganism is contained in the sample; the number of sequences of each microorganism in the sample, i.e., the relative abundance of each microorganism. As can be seen from FIG. 2, the colony structures of samples 3 and 4 at the gate classification level are significantly different from those of the other two groups.
(2) Colony Heatmap map
The community Heatmap map can reflect data information in a two-dimensional matrix or table by color change, and can visually represent the size of data values in a defined color shade. Data are often clustered for species or sample-to-sample abundance similarity as needed, and the clustered data are presented on a heatmap. As can be seen from FIG. 3, samples 3 and 4 are clearly different from the other two groups in species at the genus classification level or in the clustering of similarity in abundance between samples.
(3) Alpha diversity analysis (Alpha-diversity)
Alpha diversity includes chao index, ace index, shannon index, simpson index, and the like. The larger the first 3 indices and the smaller the last index, indicating a greater abundance of species in the sample.
The chao index and the ACE index reflect the abundance of the community (species richness) in the sample, i.e. simply the number of species in the community, regardless of the abundance of each species in the community. The dilution curve corresponding to these 2 indices may also reflect whether the sample sequencing amount is sufficient. If the curve tends to be flat or reaches a plateau, the sequencing depth can be considered to cover substantially all the species in the sample; conversely, it indicates that the species diversity in the sample is higher, and there are more species that are not detected by sequencing.
As can be seen from FIGS. 4 and 5, the number of colonies in samples 3 and 4 was significantly smaller than in the other two groups.
The shannon index and the simpson index reflect the diversity (species diversity) of the community, and are influenced by the abundance (species richness) and uniformity (species evenness) of species in the sample community. The greater the homogeneity of the species in the population, the greater the diversity of the population.
As can also be seen from FIGS. 6 and 7, samples 3 and 4 are significantly less abundant and diverse in colonies than the other two groups.
(4) Beta diversity analysis (Beta-diversity)
Unlike Alpha diversity analysis, beta diversity (Beta diversity) analysis is used to compare the magnitude of the difference in species diversity between a pair of samples. And analyzing the content of each group in the sample, and further calculating Beta diversity values among different samples.
Various indices may be used to measure Beta diversity, commonly used are Bray-Curtis, weighted unifrrac, unweighted unifrrac.
1) Weighted analysis of (un) weighted
The UniFrac analysis uses evolutionary information between sample sequences to compare environmental samples for significant differences in microbiota within a particular evolutionary lineage. The UniFrac can be used for evaluating and analyzing beta diversity, namely, the samples are compared and analyzed pairwise to obtain a UniFrac distance matrix between the samples.
unweighted unifrac can detect the presence of variations between samples, and weighted unifrac can further quantify variations across different lineages between samples.
TABLE 7 weighted unifrac diversity matrix
1 1_mud 2 2_mud 3 4
1 0 0.538713 0.185855 0.561589 0.795779 0.776554
1_mud 0.538713 0 0.560805 0.320173 0.774647 0.720011
2 0.185855 0.560805 0 0.604718 0.8038 0.790132
2_mud 0.561589 0.320173 0.604718 0 0.689335 0.650615
3 0.795779 0.774647 0.8038 0.689335 0 0.087576
4 0.776554 0.720011 0.790132 0.650615 0.087576 0
Visualizing table 7 can result in fig. 8;
TABLE 8 unweighted unifrac diversity matrix
Figure RE-GDA0003467824740000171
Figure RE-GDA0003467824740000181
Visualizing Table 8 results in FIG. 9;
as can be seen from tables 7, 8, and 9, the red color with a heavier color represents a large difference in the microbial population, i.e., the samples 3 and 4 are different from the samples 1 and 2 in different pedigrees; the difference of the color of orange or orange is intermediate, i.e. the difference between the samples 3 and 4 and the samples 1 and 2 is slightly smaller than that of the samples 1 and 2, but still has a certain difference.
2) Weighted. Unifrac-based PCoA
The distance matrix obtained by Unifrac analysis can be used for various analysis methods, and the similarity and difference of microorganism evolution in samples in different environments can be visually displayed through PCoA analysis by a multivariate statistical method.
PCoA (principal co-ordinates analysis) is a visualization method for studying data similarity or difference, and after sorting through a series of eigenvalues and eigenvectors, and selecting eigenvalues mainly ranked in the first few digits, PCoA can find the most dominant coordinate in the distance matrix, and as a result, a rotation of the data matrix does not change the mutual positional relationship between sample points, but only the coordinate system. Differences between individuals or populations can be observed by PCoA.
As can be seen from fig. 10 and 11, samples 3 and 4 were significantly different from the other four samples in terms of microbial evolution in the first principal component, and samples 1 and 2 were significantly different from samples # 1 and # 2 in the second principal component, with samples 3 and 4 therebetween.
3) Unifrac-based multi-sample similarity tree analysis
The distance matrix obtained by Unifrac analysis can be used for various analysis methods, and by graphical visualization processing such as construction of an evolutionary tree by a non-weighted group mean method UPGMA in Hierarchical clustering (Hierarchical clustering), the similarity and the difference of microorganism evolution in samples in different environments can be visually displayed.
UPGMA (Unweighted pair group method with arithmetric mean) assumes the same rate of variation for all nucleotides/amino acids during evolution, i.e.there is one molecular clock. The evolutionary distance between the samples can be observed through the distance of the branches and the distance of the clusters.
As can be seen from fig. 12 and 13, samples 3 and 4 are not on one branch with the remaining four samples, and thus have a large difference.
4) Non-metric multidimensional scaling analysis based on (un) weighted
The non-metric multidimensional scaling method is a data analysis method which simplifies the research objects (samples or variables) in multidimensional space into low-dimensional space for positioning, analysis and classification, and simultaneously reserves the original relation among the objects. The method is suitable for the situation that accurate similarity or dissimilarity data among research objects cannot be obtained and only hierarchical relation data among the research objects can be obtained. The method is characterized in that the method reflects the species information contained in the sample on a multidimensional space in a point form, and the difference degree between different samples is reflected by the distance between the point and the point, so that the space positioning point diagram of the sample is finally obtained. As can be seen from fig. 14 and 15, the samples 3 and 4 are far from the samples 1 and 2 after weighting, and have a large difference from the mud samples # 1 and # 2.
5) Bray-Curtis distance analysis based on species information
The Bray-Curtis distance is a common indicator reflecting the difference between two colonies. The Bray-Curtis distance is calculated without considering the evolutionary distance between the sequences, and only considering the presence of species in the sample. The Bray-Curtis distance has values between 0 and 1, with larger values indicating greater differences between samples. As can be seen from fig. 16, samples 3 and 4 are different from samples 1 and 2 in the gate level in the way that the differences between the colonies are large.
6) Multi-sample similarity tree and histogram combined analysis
As can be seen from fig. 17, samples 3 and 4 are very different from the other four samples at the species level.
It can be known through the above analysis that stake 74 softens jar and goes out water and soften recovery tank water and stake western union filter play water, stake 74 comes water, softens jar center section of thick bamboo mud, mud bottom of the pool mud and compare, all have great difference in the fungus crowd composition and distribute: the species and the content of the microorganisms are greatly changed; the community composition difference at each classification level is large; further quantification of the samples varied across different lineages.
Taking a water sample of 2500-25000/ml of sulfate reducing bacteria at the inlet of a primary filtering device for softening and fine water produced by an oilfield on the spot, and examining the action effect evaluation tests of the bactericide (SH-2 type) described in example 1, the bactericide (SH-1 type) described in example 4 and the bactericide (SH-3 type) described in example 7, wherein the use concentrations of the bactericides are 40mg/l, 50mg/l and 60mg/l respectively; the specific bactericidal effect is shown in table 9 below.
TABLE 9 indoor sterilizing effect of SH-1 type, SH-2 type and SH-3 type bactericides
Figure RE-GDA0003467824740000201
Table 9 shows that the SRB bacteria are controlled within 25/mL under the condition that the three bactericides of example 1, example 4 and example 7 are added with 40-50 mg/indoor drug; the bactericidal effect of the bactericide is obviously better than that of a 1227 bactericide.
The bactericidal effect of the bactericide was examined in the field test, and the results are shown in the following tables 10, 11 and 12.
TABLE 10 field test dosing effect of the germicidal formulations described in example 1
Figure RE-GDA0003467824740000202
Figure RE-GDA0003467824740000211
2019.10.8-2019.10.20, the medicament optimization test is carried out after the filter for 13 days continuously on site, and as seen from table 10, the bactericide described in example 1 has good effect in controlling the SRB bacteria in the sewage of the pile 74 station, and the SRB bacteria are controlled within 6/mL when the chemical adding amount of the reinjection water is 45mg/L, so that the production requirement is met.
TABLE 11 field test dosing effect of the germicidal formulations described in example 4
Figure RE-GDA0003467824740000212
Figure RE-GDA0003467824740000221
2019.11.1-2019.11.21, the medicament optimization test is carried out after the filter for 13 days continuously on site, and as seen from table 11, the bactericide in example 4 has good effect in controlling the SRB bacteria in the sewage of the pile 74 station, and the SRB bacteria are controlled within 25/mL when the chemical adding amount of the reinjection water is 45mg/L, so that the production requirement is met.
TABLE 12 on-site test effect of the germicide described in example 7
Figure RE-GDA0003467824740000222
2019.12.25-2020.1.6, the medicament optimization test is carried out after the filter for 13 consecutive days on site, and as seen from table 12, the bactericide described in example 7 has good effect in controlling the SRB bacteria in the sewage of the pile 74 station, and the SRB bacteria are controlled within 25/mL when the chemical adding amount of the reinjection water is 45mg/L, so that the production requirement is met.
2019.12.18-2021.3.24, the water quality of 74 stations transported out of the field is tested 15 times on the field, and as seen from table 13, the bactericide has good effect in controlling the SRB bacteria in the 74-station sewage.
Meter 13 pile 74 station field external transportation water quality detection effect
Figure RE-GDA0003467824740000231
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (7)

1. The sulfate reducing bacteria bactericide is characterized by comprising the following components in parts by weight: 10-40 parts of dodecyl dimethyl benzyl ammonium chloride, 0-20 parts of glutaraldehyde, 10-30 parts of A bactericide and 10-80 parts of water;
the A bactericide is any one of alkyl diquaternary ammonium salt, dodecyl guanidine hydrochloride and hydroxypropyl gemini quaternary ammonium salt modified guanidine.
2. The sulfate-reducing bacteria bactericide of claim 1, wherein the bactericide comprises the following components in parts by weight:
10-30 parts of dodecyl dimethyl benzyl ammonium chloride, 10-20 parts of alkyl bis-quaternary ammonium salt and 50-80 parts of water.
3. The sulfate-reducing bacteria fungicide of claim 2, wherein said alkyl bis-quaternary ammonium salt has an alkyl group of 10 to 18 carbon atoms.
4. The sulfate-reducing bacteria bactericide of claim 1, wherein the bactericide comprises the following components in parts by weight:
10-20 parts of dodecyl dimethyl benzyl ammonium chloride, 10-20 parts of dodecyl guanidine hydrochloride, 4-15 parts of glutaraldehyde and 45-76 parts of water.
5. The sulfate-reducing bacteria bactericide as claimed in claim 1, wherein the bactericide comprises the following components in parts by weight: 10-20 parts of dodecyl dimethyl benzyl ammonium chloride, 10-20 parts of hydroxypropyl gemini quaternary ammonium salt modified guanidine, 4-20 parts of glutaraldehyde and 40-76 parts of water.
6. The sulfate-reducing bacteria fungicide according to claim 5, wherein the number of carbon atoms of alkyl groups in the hydroxypropyl gemini quaternary ammonium salt modified guanidine is 10 to 18.
7. Use of the sulfate-reducing bacteria biocide of any one of claims 1-6 in oilfield wastewater softening treatment.
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