CN111011398A - Biological bactericide for crude oil transportation pipeline and application thereof - Google Patents
Biological bactericide for crude oil transportation pipeline and application thereof Download PDFInfo
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Abstract
The invention provides a biological bactericide for a crude oil transportation pipeline, which mainly comprises the components of alcanivorax paraguariensis and has no pathogenicity; compared with the conventional inorganic and organic bactericides, the biological bactericide has the advantages of low consumption, simple and convenient use, environmental protection and green, and belongs to an environment-friendly bactericide. The biological bactericide can improve the pH value in the environment, can effectively inhibit the microbial corrosion of metal, can reduce the corrosion rate of X70 pipeline steel by 200 times, and has no corrosion. The corrosion resistance of the metal specimen is improved with the increase of the soaking time. The biological bactericide has the principle that the pH value is changed, so that the biological bactericide is not suitable for other microorganisms to live, and the defect that the traditional bactericide is easy to generate drug resistance is overcome. The biological bactericide is used for metal protection of crude oil transportation pipelines, is simple to operate, has no requirements on the size and the shape of the pipelines, and can greatly reduce the cost of inhibiting microbial corrosion of the pipelines in petroleum enterprises as long as fluid flows through the pipelines.
Description
Technical Field
The invention belongs to the field of environmental engineering, and particularly relates to a biological bactericide for a crude oil transportation pipeline and application thereof.
Background
The metal materials used in the environment of crude oil transportation pipelines face serious microbial corrosion, which accounts for 70-80% of the total metal materials, and in the crude oil transportation pipelines, the microbial corrosion is more serious, and the corrosion perforation thereof often causes large-scale crude oil leakage, pollutes the environment, causes the price fluctuation of the crude oil, affects the national civilization, and the energy consumption and the loss caused by corrosion are up to billions of dollars each year due to the microbial corrosion, wherein the large part is caused by Sulfate Reducing Bacteria (SRB) or Iron Oxidizing Bacteria (IOB).
Among the corrosion protection techniques, organic coatings are a good way to protect metal substrates. However, coating in crude oil transportation pipelines is difficult and costly, and once damaged, corrosion of metal materials is accelerated. The use of biocides in these fluids is one of the effective methods of inhibiting microbial corrosion, but over time, the effectiveness of a single biocide is greatly reduced and eventually lost due to microbial resistance. To address this phenomenon, "cocktail therapy" has been developed, which uses several mixed bactericides, but the cost thereof is greatly increased and it is not environmentally friendly.
Therefore, the development of green and environment-friendly technical means is imperative. Biological bactericides have gained wide attention because of their environmental protection and non-toxicity. The literature search of the prior art shows that some biological bactericides have certain function of killing bacteria (Malay, a compound biological bactericide for preventing and treating grape diseases and application thereof, CN106942284B), but most biological bactericides are used in the agricultural field and can possibly cause corrosion; some of the bacteria also have the ability to form biofilms and to inhibit corrosion (songshan et al, a bio-metal corrosion inhibitor and its applications, CN 104480472 a); in addition, some biological bactericides are ammonifying bacteria, can utilize organic matters in the environment to generate a large amount of ammonia, improve the pH value in the environment, and achieve the purpose of inhibiting the bacteria and even killing the bacteria by changing the pH value in the environment.
Although the biological bactericide has the function of inhibiting or killing bacteria, whether the biological bactericide can survive in a crude oil environment or not, and meanwhile, the biological bactericide has the characteristics of inhibiting bacteria and killing bacteria and not causing corrosion, and is the biological bactericide for the crude oil transportation pipeline. Therefore, the search for a biological bactericide which can survive in a crude oil environment, has bacteriostatic and bactericidal effects, and does not cause corrosion is a problem to be solved in the art.
Disclosure of Invention
In order to solve the technical problems, the invention provides a biological bactericide for a crude oil transportation pipeline, which can effectively kill bacteria by increasing the pH value in the environment, reduce the corrosion rate and the pitting occurrence rate of metal materials in the pipeline, and reduce the corrosion rate by about 200 times for X70 pipeline steel.
In order to achieve the purpose, the invention adopts the technical scheme that: a biological bactericide for crude oil transportation pipelines contains Alkylia poachanii or Alkylia poacharii and molybdate.
Preferably, the concentration of viable bacteria of the alcanivorax poeciloti in the biological bactericide is not less than 1 x 108～5×108CFU/ml; the mass percentage of the molybdate is 4-8%.
The invention also provides a preparation method of the biological bactericide for the crude oil transportation pipeline, which comprises the following steps:
inoculating paragonimus patorii in a culture medium, and performing shake culture at 26-37 ℃ to obtain a bacterial liquid, namely the biological bactericide;
or inoculating the paradise alcanivorax in a culture medium, performing shake culture at 26-37 ℃ to obtain a bacterial liquid, adding molybdate into the bacterial liquid, and uniformly stirring to obtain the biological bactericide.
Preferably, the concentration of the viable bacteria is 1 x 108～5×108CFU/ml; the mass percentage of the molybdate is 4-8%.
The invention also provides application of the biological bactericide for the crude oil transportation pipeline in inhibiting microbial corrosion in the petroleum transportation pipeline prepared from the metal material.
Preferably, the biological bactericide is diluted by 500-1000 times, and the diluted biological bactericide is directly added into a required crude oil transportation pipeline.
Preferably, the metal material is one of carbon steel, low alloy steel and stainless steel.
The invention has the beneficial effects that:
(1) the invention provides a novel biological bactericide, which mainly comprises alcanivorax paraguariensis serving as a main component and has no pathogenicity; compared with the conventional inorganic and organic bactericides, the biological bactericide has the advantages of low consumption, simple and convenient use, environmental protection and green, and belongs to an environment-friendly bactericide.
(2) The biological bactericide can improve the pH value in the environment, kill bacteria, effectively inhibit the microbial corrosion of metal, reduce the corrosion rate of X70 pipeline steel by 200 times, and has no corrosion. The corrosion resistance of the metal specimen is improved with the increase of the soaking time.
(3) The biological bactericide has the principle that the pH value is changed, so that the biological bactericide is not suitable for other microorganisms to live, and the defect that the traditional bactericide is easy to generate drug resistance is overcome.
(4) The biological bactericide is used for metal protection of crude oil transportation pipelines, is simple to operate, has no requirements on the size and the shape of the pipelines, and can greatly reduce the cost of inhibiting microbial corrosion of the pipelines in petroleum enterprises as long as fluid flows through the pipelines.
Drawings
FIG. 1 is a diagram showing the relative contents of Alkylidenivorax pokugenum and sulfate-reducing bacteria in the experimental group system of example 3.
FIG. 2 is a graph showing the change in pH in the experimental and control systems of example 3. .
FIG. 3 is the Nyquist plot of the electrochemical impedance spectra for the experimental and control systems of example 4 (where A is M2 experimental and B is M1 control).
FIG. 4 shows that the inoculation ratio of SRB to Alkylophagus Podochii in example 5 is 10: 1 nyquist plot of electrochemical impedance spectroscopy.
FIG. 5 shows that the inoculation ratio of SRB to Alkylophagus Podochii in example 6 is 100: 1 nyquist plot of electrochemical impedance spectroscopy.
FIG. 6 shows the inoculation ratio of SRB to Alkylophagus Podochii in example 7 is 1000: 1 nyquist plot of electrochemical impedance spectroscopy.
FIG. 7 is a graph showing polarization impedances in examples 5, 6 and 7.
FIG. 8 is a graph of pitting corrosion on the X70 pipeline steel of example 8 after immersion in a system containing only SRB.
FIG. 9 is a graph showing the pitting corrosion on the X70 pipeline steel in example 8 after immersion in a system containing Alkylinovorin Podochii and SRB.
FIG. 10 is a graph of the growth of Alkylia podochii in a crude oil environment.
Detailed Description
In order to more concisely and clearly demonstrate technical solutions, objects and advantages of the present invention, the following detailed description of the present invention is provided with reference to specific embodiments and accompanying drawings.
The Alcanivorax borkumens strain employed in the examples was purchased from China center for culture Collection of Marine microorganisms (address: Ministry of Ogaku, Ltd. No. 178) and designated MCCC-1A 01031. The purchased strains were stored in a-80 ℃ glycerol medium mixture (20% glycerol + 80% 2216E broth, V/V).
EXAMPLE 1 preparation of Biocide
Thawing Alkylidea Podocosa stored in 2216E liquid culture medium containing 20% glycerol at-80 deg.C at 25 deg.C, inoculating 1000 μ l into 2216E liquid culture medium, shake culturing at 37 deg.C and 120r/min for 24 hr to obtain bacterial liquid, diluting to 1 × 108CFU/ml, and obtaining the biological bactericide.
Example 2 inhibition of Corrosion bacteria by Biobactericides
0.001kg of the biological bactericide prepared in example 1 is diluted by 500-fold and added into postgate culture medium, and then Sulfate Reducing Bacteria (SRB) are added, wherein the addition amount of the Sulfate Reducing Bacteria (SRB) is the same as that of the bactericide, and the ratio of the addition amount of the Sulfate Reducing Bacteria (SRB) to the bactericide is 1: 1. In this example, an experimental group containing both a bactericide (alcanivorax pokugenensis) and SRB and a control group containing only SRB were provided.
EXAMPLE 3 determination of relative amounts of two bacteria and pH in the System
50ml samples of the experimental group and the control group of example 2 were taken at 1 day, 3 days, 5 days, 7 days, 9 days, 11 days, and 14 days, respectively, and sent to Meiji Bio Inc. for biodiversity examination, and the pH of both groups was measured.
Example 4 Corrosion inhibition Performance of the Fungicide on X70 pipeline Steel
X70 pipeline steel was used as the metallic material. The metal sample was cut into a 1cm by 1cm square, the wires were connected and encapsulated with epoxy, exposing a 1cm by 1cm work surface. And (3) gradually polishing the sample to 1200 meshes of abrasive paper by using water abrasive paper, placing the sample in alcohol for ultrasonic cleaning, and then placing the sample under an ultraviolet lamp for irradiation for 1h for sterilization. Control and experimental groups were set, with 12 metal samples per group.
Control sample M1: the metal sample was placed in a Erlenmeyer flask containing SRB but no germicide, and the flask was placed in a biochemical incubator at 37 ℃ and 120 rpm/min.
Experimental group sample M2: a metal sample was placed in a Erlenmeyer flask containing the experimental group solution of example 2, and the flask was placed in a biochemical incubator at 37 ℃ and at 120 rpm/min.
Samples treated for 1 day, 3 days, 5 days, 7 days, 9 days, 11 days and 13 days are taken out from the experimental group and the control group respectively, and the effect of the bactericide on inhibiting the microbial corrosion is evaluated by adopting alternating current impedance. The control sample was designated as M1 and the experimental sample was designated as M2.
The specific test method of the alternating current impedance comprises the following steps:
the alternating current impedance spectrum is measured by adopting an Autolab302 electrochemical workstation (PGSTAT302) of Wantong Switzerland, a platinum electrode is adopted as an auxiliary electrode, a calomel electrode is adopted as a reference electrode, a metal sample is adopted as a working electrode, a test medium is a sterile postgate culture medium, and the test frequency range is 105Hz-10-2Hz。
The corrosion inhibition resistance is measured by means of an alternating current impedance. The corrosion inhibition effect is obtained by measuring the polarization resistance, and the larger the polarization resistance is, the better the effect of the bactericide on inhibiting the microbial corrosion is.
The relative amounts of the two bacteria varied as shown in FIG. 1, demonstrating that the biocide of the invention kills most of the SRB at day 3. FIG. 2 shows the change in pH, which is seen at day 3 when the pH has rapidly increased to around 9.0, and is not suitable for the survival of most microorganisms. The electrochemical impedance spectroscopy data for 13 days are shown in FIG. 3. The arc of impedance in all systems has increased with longer soak times.
Example 5
The other conditions were the same as in example 2, except that the ratio of SRB to alcanivorax paraguariensis inoculation was changed to 10: 1. according to the method of example 4, see fig. 4 and 7, the X70 pipeline steel also shows good corrosion resistance within 14 days.
Example 6
The other conditions were the same as in example 2, except that the ratio of SRB to alcanivorax paraguariensis inoculation was changed to 100: 1. according to the method of example 4, as shown in fig. 5 and 7, the X70 pipeline steel also shows good corrosion resistance within 14 days.
Example 7
The other conditions were the same as in example 2, except that the ratio of SRB to alcanivorax paraguariensis inoculation was changed to 1000: 1. according to the method of example 4, as shown in fig. 6 and 7, the X70 pipeline steel also showed a decrease in corrosion resistance within 14 days.
EXAMPLE 8 pitting resistance Effect of Biocide
X70 pipeline steel was used as the metallic material. The metal samples were cut into 1cm by 1cm squares and encapsulated with epoxy, exposing a 1cm by 1cm work surface. And (3) gradually polishing the sample to 1200 meshes of abrasive paper by using water abrasive paper, placing the sample in alcohol for ultrasonic cleaning, and then placing the sample under an ultraviolet lamp for irradiation for 1h for sterilization. Control and experimental groups were set, with 2 metal samples per group.
Control sample M1: the metal sample is placed in a triangular flask containing an SRB system, and the flask is placed in a biochemical incubator, the temperature is set to 37 ℃, and the rotating speed is 120 rpm/min.
Experimental group sample M2: the metal sample was placed in a Erlenmeyer flask containing the system solution of example 2, and the flask was placed in a biochemical incubator at 37 ℃ and 120 rpm/min.
From the experimental group and the control group, 14-day-processed samples were taken, and the product films on the surfaces of the samples were removed with a removing solution (100ml of 37.5% hydrochloric acid, 1g N, N-dibutylthiourea), followed by observation of the surface pitting conditions in a white light interferometer.
The M1 surface pitting condition is shown in FIG. 8, the number of pitting pits on the surface pitting condition is large, and the diameter of the pitting pit is also large. The pitting condition of the M2 surface is shown in FIG. 9, and almost no pitting pits exist on the pitting condition, and the sample is still marked when the sample is initially sanded. Therefore, the bactericide can well protect metal materials from pitting influence caused by microbial corrosion.
Example 9
The biological bactericide comprises alcanivorax poaquae and molybdate, and the preparation method comprises the following steps:
inoculating paragonimus island into a culture medium, performing shake culture at 26 ℃ to obtain a bacterial liquid, adding molybdate into the bacterial liquid, and uniformly stirring to obtain the biological bactericide. The concentration of viable bacteria in the bacterial liquid is 5 multiplied by 108CFU/ml, the weight percentage of molybdate is 4%.
Example 10
The biological bactericide comprises alcanivorax poaquae and molybdate, and the preparation method comprises the following steps:
inoculating paragonimus island into a culture medium, performing shake culture at 37 ℃ to obtain a bacterial liquid, adding molybdate into the bacterial liquid, and uniformly stirring to obtain the biological bactericide. The concentration of viable bacteria in the bacterial liquid is 5 multiplied by 108CFU/ml, the weight percentage of molybdate is 8 percent.
The biological bactericide prepared in examples 9 and 10 was verified for its anti-corrosive effect. X70 pipeline steel was used as the metal material. The metal samples were cut into 1cm by 1cm squares and encapsulated with epoxy, exposing a 1cm by 1cm work surface. And (3) gradually polishing the sample to 1200 meshes of abrasive paper by using water abrasive paper, placing the sample in alcohol for ultrasonic cleaning, and then placing the sample under an ultraviolet lamp for irradiation for 1h for sterilization. The control group was set up with experimental group 1 (example 9) and experimental group 2 (example 10), with 2 metal samples per group, and the results are shown in table 1.
Control group: the metal sample was placed in the system of example 2 in which sulfate-reducing bacteria (SRB) were cultured alone;
experimental group 2: placing a metal sample in a system containing the biocide prepared in example 9 and SRB;
experimental group 3: placing a metal sample in a system containing the biocide prepared in example 10 and SRB;
table 1: the biological bactericide prepared in examples 9 and 10 has a corrosion inhibition effect on metal pipelines
Example 11
The growth curve of the alkane Podocaine in the petroleum is shown in figure 10, which proves that the alkane Podocaine can survive for 14 days in the petroleum and still maintain high biomass.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (7)
1. The biological bactericide for the crude oil transportation pipeline is characterized by comprising alcanivorax poachariiformis or comprising alcanivorax poachariiformis and molybdate at the same time.
2. The biological bactericide for crude oil transportation pipelines according to claim 1, wherein the viable bacteria concentration of Alanivorax pokuchii in the biological bactericide is not less than 1 x 108～5×108CFU/ml; the mass percentage of the molybdate is 4-8%.
3. A preparation method of a biological bactericide for a crude oil transportation pipeline is characterized by comprising the following steps:
inoculating paragonimus patorii in a culture medium, and performing shake culture at 26-37 ℃ to obtain a bacterial liquid, namely the biological bactericide;
or inoculating the paradise alcanivorax in a culture medium, performing shake culture at 26-37 ℃ to obtain a bacterial liquid, adding molybdate into the bacterial liquid, and uniformly stirring to obtain the biological bactericide.
4. The method according to claim 3, wherein the viable bacteria concentration is 1X 108～5×108CFU/ml; the mass percentage of the molybdate is 4-8%.
5. An application of the biological bactericide for the crude oil transportation pipeline in inhibiting the microbial corrosion of the petroleum transportation pipeline made of metal material.
6. The method of application according to claim 5, wherein the method is: diluting the biological bactericide by 500-1000 times, and directly adding the diluted biological bactericide into a required crude oil transportation pipeline.
7. The method of use of claim 5, wherein the metallic material is one of carbon steel, low alloy steel, stainless steel.
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