CN103109850A - Composite bactericide for efficiently inhibiting iron bacteria - Google Patents
Composite bactericide for efficiently inhibiting iron bacteria Download PDFInfo
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- CN103109850A CN103109850A CN2013100360623A CN201310036062A CN103109850A CN 103109850 A CN103109850 A CN 103109850A CN 2013100360623 A CN2013100360623 A CN 2013100360623A CN 201310036062 A CN201310036062 A CN 201310036062A CN 103109850 A CN103109850 A CN 103109850A
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Abstract
The invention relates to a composite bactericide for efficiently inhibiting iron bacteria. The bactericide contains quaternary ammonium salt and quaternary phosphonium salt, preferably quaternary ammonium salt, 1227, glutaric dialdehyde and quaternary phosphonium salt. More preferably, the bactericide comprises the following components in percentage by mass: 35-65% of quaternary ammonium salt, 1-18% of 1227, 5-35% of glutaric dialdehyde, 0.5-12% of quaternary phosphonium salt and the balance of water. The bactericide is specifically used for overcoming pipeline erosion caused by the reproduction of a large amount of corrosive microorganisms in oilfield produced water, especially has excellent killing effect on iron bacteria which are difficult to kill with a common bactericide, and simultaneously has favorable water solubility; after being used in water, the water quality is changed in a complicated manner (the pH value fluctuates, the temperature fluctuates, the mineralization degree is high and the oil index is high); and the bactericide is low in dosage, and an addition amount of 30mg/L or above can achieve the purpose of favorably inhibiting growth and reproduction of iron bacteria.
Description
Technical field
The present invention relates to ground, oil field technical field of chemistry, particularly, the present invention relates to the compound disinfectant of a kind of efficient inhibition iron bacteria.
Background technology
In the oilfield sewage system, sulfate reducing bacteria (SRB), saprophytic bacteria (TGB) and three kinds of microorganisms of iron bacteria (IB) are growth and breeding in same environment often.TGB bacterium amount reproduction, and generate biomembrane at hardware or pipeline surface, common " the deposition knurl " that forms metal surface such as biomembrane and corrosion of metal product, inorganic matter deposition, metal surface under knurl becomes the anode region of oxygen deprivation, outer other metal surfaces of knurl become the cathodic region of oxygen enrichment, and this local oxygen concentration cell effect very easily makes metal under knurl form pit.Simultaneously, the anoxic zone under knurl just in time provides the place of growth, breeding for the anaerobic bacterium, and the biological chemistry action by anaerobes such as SRB is corrosion pipeline gradually.
Iron-oxidizing bacterium (iron-oxidizing bacteria), claim again iron bacteria (iron bacteria), is a kind of aerobic heterotroph, is present in the environment containing aerobic and iron.In the water that is 1 ~ 6mg/L in total iron amount, the iron bacteria breeding is vigorous, iron bacteria be take organic matter as nutrient source, its growth needs organic matter, the organic compound of preference iron and manganese, can utilize ferrous Catalytic Oxygen is changed into to the energy that the reaction of high price compound discharges to meet its vital movement needs, and iron and (or) Mn oxide is deposited in the thalline pod membrane, sheath is interior or the cell exocrine thing on.In oil field, common iron bacteria kind has Leptothrix (Leptothrix), Sphaerotilus (Sphaerotilus), Gallionella (Gallionella), Crenothrix (Grenothrix) and sheath iron bacteria (Siderocapsa), wherein with Leptothrix (Leptothrix) and football shirt bacterium number (Sphaerotilus), distribute the most extensive, quantity is maximum, the ecological significance maximum.Iron bacteria can secrete oxidoreductase, and oxidoreductase is attached to extracellular, and the oxidation ferrous iron becomes insoluble hydroxide; The part iron bacteria is transferred to the iron of absorption in bacterial body and reoxidizes, and therefrom obtains biological growth and breed required energy; For organic iron, bacterium discharges it by utilizing its organic principle, then carries out oxidation.
There is much harm in iron bacteria in the industry of oil field, as accelerate the corrosion of pipeline, obstruction on stratum etc. while causing delivery equipment and pipeline and re-injection, so while in oil field, re-injection water and outer draining being processed, iron bacteria quantity is a strict index of controlling, and usually need to add bactericide to control breeding and the quantity of iron bacteria.What in the recovered water of ground, oil field, commonly use at present is mainly non-oxidizable bactericide, mainly comprises quaternary ammonium salt (as 1227); Quaternary alkylphosphonium salt (as THPS); Aldehyde, ketone (glutaraldehyde, isothiazolinone etc.); The guanidine class, built agent of organic sulfur oxide and various monomer bactericide etc., find when Oil Field is used, through using and screening for many years, above-mentioned bactericide mainly has inhibitory action preferably to SRB, and very limited for the inhibition ability of iron bacteria.In domestic certain oil field extracted water, due to a large amount of interpolations of acid antisludging agent, the pH value descends, and causes the concentration sharp increase of iron ion in medium and growing in a large number of iron bacteria, adds bactericide very weak to the inhibition ability of iron bacteria.
CN 102726446A discloses a kind of circulation high efficiency composition bactericide, and this high efficiency composition material of germicide component and percentage by weight are: glutaraldehyde 20%-30%, quaternary alkylphosphonium salt 30%-40%, isothiazolinone 10%-20%, deionized water 20%-30%.But this bactericide to the inhibition ability of iron bacteria a little less than, and be unsuitable for oil field produced water system.
Therefore, research and develop and a kind of iron bacteria in oil field extracted water is had to the technical barrier that efficient inhibiting bactericide is affiliated field.
The present invention is in conjunction with experiment and the field situation, in conjunction with the special construction of iron bacteria and the sterilization mechanism of different bactericide, develop in Oil Field sewage the bactericide that when multiple-microorganism exists jointly, corrosivity microorganism especially iron bacteria is had to efficient inhibition ability.
Summary of the invention
For the deficiencies in the prior art, one of purpose of the present invention is to provide the compound disinfectant of a kind of efficient inhibition iron bacteria.This bactericide specialty is for corrosive pipeline that in oil field extracted water, the macro-corrosion microbial reproduction causes, especially the iron bacteria that is difficult to kill for common fungicide has the good ability of killing, the while good water solubility, use complicated (the pH value fluctuation of change of water quality, temperature fluctuation, salinity is high, the oils index is high), and dosing is little, can reach the purpose of good inhibition iron bacteria growth and breeding.
Described bactericide contains quaternary ammonium salt and quaternary alkylphosphonium salt.
Because iron bacteria has the structure of pod membrane or sheath, therefore the stripping ability for bactericide requires higher.Double-chain quaternary ammonium salt has the capillary ability of water-soluble and good preferably reduction, also has the function of the detrimental effects such as opposing anion surfactant, hard water, albumen organic matter, and its effect of killing livestock is stronger than strand quaternary ammonium salt, and the spectrum of killing livestock is wider; Quaternary alkylphosphonium salt is to the absorption of bacterium and peel off many that infiltration capacity can be strong than common quaternary ammonium salt and aldehydes bactericide, penetrable iron bacteria pod membrane after contacting with bacterium, change bacterium endochylema membrane permeability, important enzyme and nutriment in thalline exosmosed, breathing and the glycolytic cycle of pathogenic microorganism are obstructed, the mycoprotein sex change, water cracks pathogene or melts to split and dead to infiltrating in thalline, thereby presents bactericidal action.
Preferably, described bactericide comprises that quaternary ammonium salt, 1227(are dodecyl benzyl dimethyl ammonium chloride), glutaraldehyde and quaternary alkylphosphonium salt.
Preferably, described bactericide comprises according to mass percent:
The content of described quaternary alkylphosphonium salt can be preferably 38 ~ 60% for such as 35.1%, 35.2%, 35.5%, 36%, 37%, 39%, 41%, 45%, 50%, 54%, 56%, 59%, 61%, 63%, 64% etc., is particularly preferably 42 ~ 55%.
Described 1227 content can be preferably 3 ~ 13% for such as 1.1%, 1.2%, 2%, 2.%, 3.1%, 4%, 6%, 9%, 11%, 12%, 14%, 16%, 17% etc., is particularly preferably 5 ~ 10%.
The content of described glutaraldehyde can be preferably 8 ~ 32% for such as 5.1%, 5.2%, 6%, 7%, 9%, 11%, 15%, 20%, 27%, 29%, 30%, 31%, 3%, 34% etc., is particularly preferably 10 ~ 28%.
The content of described quaternary alkylphosphonium salt can be preferably 0.8 ~ 8% for such as 0.6%, 0.7%, 0.9%, 1.1%, 1.2%, 2%, 4%, 6%, 7%, 9%, 10%, 11% etc., is particularly preferably 1 ~ 5%.
Preferably, described bactericide comprises according to mass percent:
Preferably, described bactericide comprises according to mass percent:
Particularly preferably, described bactericide is composed of the following components according to mass percent:
Described quaternary ammonium salt can be the known any quaternary ammonium salt in affiliated field, such as a kind or the combination of at least 2 kinds in alkyl benzyl dimethyl ammonium halide, zephiran or Dialkyl dimethyl ammonium chloride (such as two octyldimethyl ammonium chloride, two dodecyl dimethyl ammonium chloride or octyl group dodecyl dimethyl ammonium chloride etc.), it can be also the quaternary ammonium salt of new research and development.
Preferably, described quaternary ammonium salt structure is as shown in the formula (I):
Wherein, R
1and R
2for replacing or unsubstituted C5 ~ C22 alkyl or replacement or unsubstituted C6 ~ C22 aryl, X is Cl, Br or I independently.
Preferably, R
1and R
2for replacing or unsubstituted C5 ~ C22 alkyl, further preferred independently, R
1and R
2be unsubstituted C6 ~ C20 alkyl independently, particularly preferably, R
1and R
2be unsubstituted C8 ~ C18 alkyl independently.
Preferably, X is Cl or Br.
Particularly preferably, described quaternary ammonium salt structure is as shown in the formula (II):
Wherein, the integer that n is 8 ~ 18, X is Cl or Br.
Described quaternary alkylphosphonium salt can be the known any quaternary alkylphosphonium salt in affiliated field, four hydroxyalkyl sulfuric acid phosphorus for example, tributyl phosphorus with a long alkyl, Ethylbenzyl trialkyl phosphorus chloride, trimethyl quaternary alkylphosphonium salt (such as octadecyl trimethyl quaternary alkylphosphonium salt etc.) with single long alkyl chain, for example, with the dimethyl quaternary alkylphosphonium salt of two long alkyl chains (myristyl trimethyl phosphorus chloride, two decyl dimethyl chlorination phosphorus etc.), to Ethylbenzyl dimethyl chain alkyl quaternary alkylphosphonium salt, quaternary alkylphosphonium salt (such as three-(3-hydroxypropyl)-cetyl quaternary alkylphosphonium salt etc.) with a chain alkyl and three hydroxyalkyls, anionic group is BF
4 -and PF
6 -quaternary alkylphosphonium salt, alkoxy-modified quaternary alkylphosphonium salt, ethylidene ether modification quaternary alkylphosphonium salt or polyether-modified quaternary alkylphosphonium salt in a kind or the combination of at least 2 kinds, also can be the quaternary alkylphosphonium salt of new research and development.
Preferably, described quaternary alkylphosphonium salt structure is as shown in the formula (III):
Wherein, R
3, R
4and R
5be replacement or unsubstituted C1 ~ C7 alkyl, replacement or unsubstituted C2 ~ C7 unsaturated alkyl or replacement or unsubstituted phenyl, R independently
6for replacing or unsubstituted C8 ~ C20 alkyl or replacement or unsubstituted C8 ~ C20 aryl, Y is Cl, Br or I.
Preferably, R
3, R
4and R
5for replacing or unsubstituted C2 ~ C7 unsaturated alkyl, further preferred independently, R
3, R
4and R
5be unsubstituted C3 ~ C6 unsaturated alkyl, particularly preferably R independently
3, R
4and R
5for-C
4h
5.
Preferably, R
6for replacing or unsubstituted C8 ~ C20 alkyl, more preferably unsubstituted C10 ~ C18 alkyl, be particularly preferably unsubstituted C11 ~ C16 alkyl.
Preferably, Y is Cl or Br, is particularly preferably Cl.
Particularly preferably, described quaternary alkylphosphonium salt structure is suc as formula shown in (IV):
Preferably, described bactericide comprises that quaternary ammonium salt, 1227(are dodecyl benzyl dimethyl ammonium chloride), glutaraldehyde and quaternary alkylphosphonium salt, wherein, described quaternary ammonium salt structure as shown in the formula (II):
Described quaternary alkylphosphonium salt structure is suc as formula shown in (IV):
Particularly preferably, described bactericide is composed of the following components according to mass percent:
Wherein, described quaternary ammonium salt structure is as shown in the formula (II):
Described quaternary alkylphosphonium salt structure is suc as formula shown in (IV):
the integer that m is 11 ~ 16.
Described 1227 is dodecyl benzyl dimethyl ammonium chloride, it is a kind of cationic surfactant, belong to non oxidizing bactericide, there is wide spectrum, efficient sterilization algae removal ability, can effectively control bacterium algae propagation and foundry loam growth in water, and there is the effect of peeling off of good foundry loam and certain dispersion, osmosis, have simultaneously certain deoil, deodorizing capability and corrosion inhibition, one of ordinary skill in the art can, by commercially available acquisition, also can prepare according to prior art/new technology.
The preparation method of bactericide of the present invention can be simple mixing, for example adopts mixer to be mixed with and obtains.One of ordinary skill in the art can select suitable preparation method as required.
One of purpose of the present invention also is to provide a kind of described efficient purposes that suppresses the bactericide of iron bacteria.
The compound disinfectant of described efficient inhibition iron bacteria can be used for oil field extracted water, for the inhibition of the iron bacteria that grows in a large number and kill.
Described oil field extracted water mainly refers to the sewerage after water-oil separating in oil-field flooding displacement of reservoir oil production practice, after chemistry engineering department, ground, oil field reason is up to standard, needs re-injection underground.Owing to adopting involving great expense of injection system, complex structure, therefore for preventing that oil field reinjection water from injecting underground rear microorganism and growing in a large number corrosion water-carriage system and sleeve pipe, cause technology pipeline leakage or casing corrosion perforation, need to add on ground the chemical agents such as corrosion inhibiter, bactericide.Bactericide of the present invention has good killing and the inhibition ability for iron bacteria, good water solubility, and strong to water quality adaptability, the ground recovered water system of especially applicable high oil-containing, high salinity and pH value and temperature fluctuation complexity, there is efficiently the advantages such as low toxicity.
The water quality characteristics such as, oils index height high for pH value fluctuation in oil field extracted water, temperature fluctuation, salinity, bactericide of the present invention in actual use, by the synergistic effect of various medicament kind and content inherence in formula, make this formula there are the especially characteristics of iron bacteria of corrosivity microorganism of killing in oil field extracted water of low dosage, effective.
The compound disinfectant of efficient inhibition iron bacteria of the present invention can be used for the Treatment of Industrial Water field, particularly the wide circulation of variation water quality scope.
One of purpose of the present invention also is to provide a kind of described efficient using method that suppresses the compound disinfectant of iron bacteria.
The compound disinfectant of described efficient inhibition iron bacteria is in oil field extracted water, and by possessing watermeter, its dosage is more than 30mg/L, and more preferably 30 ~ 80mg/L, be particularly preferably 30 ~ 50mg/L.
The compound disinfectant of efficient inhibition iron bacteria of the present invention when low dosage (as 30mg/L) is used efficiently (more than 99.9%) kill oil field extracted water in corrosivity microorganism iron bacteria especially, and good water solubility, (can adapt to the fluctuation of pH value to water quality adaptability is strong, temperature fluctuation, salinity is high, the oils index is high), there is efficiently the advantages such as low toxicity.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment helps to understand the present invention, should not be considered as concrete restriction of the present invention.
Embodiment 1
The prepared bactericide of the present embodiment is comprised of following component (its deal by weight): 45 parts of quaternary ammonium salts, 5 parts of dodecyl benzyl dimethyl ammonium chlorides, 20 parts of glutaraldehydes, 1 part of quaternary alkylphosphonium salt, 29 parts, water, composite mixing; Wherein, described quaternary ammonium salt structure is suc as formula shown in (V):
Described quaternary alkylphosphonium salt structure is suc as formula shown in (VI):
Bactericide prepared by the present embodiment sterilizing ability evaluation to the iron bacteria of laboratory cultures: adopt the disappearance dilution method to be undertaken by the method for stipulating in SY/T 5890-1993, its condition determination is with reference to defined terms in Q/SY 49-2007.
Concrete operations are as follows: blank water sample bacteria containing rate η>=1 * 10
3; At room temperature in water sample, inject bactericide, sterilization 4h; Water sample after sterilization and blank sample are injected in test bottle, and are cultivated in 37 ℃ of insulating boxs.Iron bacteria is cultivated 7d ~ 14d.Experiment adopts 3 pipe methods.
The calculating of sterilizing rate adopts following formula:
Experimental result is shown in Table 1.
Table 1
Adding consistency (mg/L) | Iron bacteria quantity (individual/mL) | Sterilizing rate |
The 0(blank) | 10 7 | —— |
20 | 10 6 | 90% |
30 | 10 4 | 99.9% |
40 | 10 3 | 99.99% |
50 | 10 | 99.99% |
60 | 0 | 100% |
70 | 0 | 100% |
80 | 0 | 100% |
Bactericide prepared by the present embodiment sterilization experiment to iron bacteria in certain oil field extracted water:
Certain oil field block three phase separator effluent quality feature is as shown in table 2:
Table 2
Method of testing as in the present embodiment above as described in, experimental result is as shown in table 3.
Table 3
Adding consistency (mg/L) | Sulfate reducing bacteria quantity | Saprophytic bacteria quantity | Iron bacteria quantity |
? | (individual/mL) | (individual/mL) | (individual/mL) |
The 0(blank) | 11000 | 11000 | 11000 |
50 | 25 | 60 | 15 |
100 | 0 | 0 | 0 |
Embodiment 2
The prepared bactericide of the present embodiment is comprised of following component (its deal by weight): 65 parts of quaternary ammonium salts, 1 part of dodecyl benzyl dimethyl ammonium chloride, 30 parts of glutaraldehydes, 0.5 part of quaternary alkylphosphonium salt, 3.5 parts, water, composite mixing; Wherein, described quaternary ammonium salt structure is suc as formula shown in (VII):
Described quaternary alkylphosphonium salt structure is suc as formula shown in (VIII):
Bactericide prepared by the test the present embodiment bactericidal property to iron bacteria in certain oil field extracted water, method of testing is identical with embodiment 1, and test result is as shown in table 4.
Table 4
Embodiment 3
The prepared bactericide of the present embodiment is comprised of following component (its deal by weight): 35 parts of quaternary ammonium salts, 18 parts of dodecyl benzyl dimethyl ammonium chlorides, 5 parts of glutaraldehydes, 12 parts of quaternary alkylphosphonium salts, 30 parts, water, composite mixing; Wherein, described quaternary ammonium salt structure is suc as formula shown in (IX):
Described quaternary alkylphosphonium salt structure is suc as formula shown in (X):
Bactericide prepared by the test the present embodiment bactericidal property to iron bacteria in certain oil field extracted water, method of testing is identical with embodiment 1, and test result is as shown in table 5.
Table 5
Embodiment 4
The prepared bactericide of the present embodiment is comprised of following component (its deal by weight): 40 parts of quaternary ammonium salts, 15 parts of dodecyl benzyl dimethyl ammonium chlorides, 35 parts of glutaraldehydes, 6 parts of quaternary alkylphosphonium salts, 4 parts, water, composite mixing; Wherein, described quaternary ammonium salt structure is suc as formula shown in (XI):
Described quaternary alkylphosphonium salt structure is suc as formula shown in (XII):
Bactericide prepared by the test the present embodiment bactericidal property to iron bacteria in certain oil field extracted water, method of testing is identical with embodiment 1, and test result is as shown in table 6.
Table 6
Comparative Examples
Adopt embodiment 1 product and other bactericide to carry out the contrast experiment of iron bacteria sterilizing ability.The bactericide addition is 50mg/L.Method of testing and test condition are identical with embodiment 1.Experimental result is as shown in table 7.
Table 7
Bactericide | Iron bacteria quantity (individual/mL) | Sterilizing rate |
Blank | 10 5 | —— |
HGY-B5 | 0 | 100% |
1227 | 10 5 | 0 |
Glutaraldehyde | 10 4 | 90% |
Little molecule quaternary alkylphosphonium salt | 1.5×10 4 | 85% |
Isothiazolinone | 10 4 | 90% |
From the experimental result of above embodiment and Comparative Examples, bactericide of the present invention has excellent bactericidal property to iron bacteria.
Applicant's statement, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.The person of ordinary skill in the field should understand, any improvement in the present invention, to the interpolation of the equivalence replacement of each raw material of product of the present invention and auxiliary element, the selection of concrete mode etc., within all dropping on protection scope of the present invention and open scope.
Claims (10)
1. an efficient compound disinfectant that suppresses iron bacteria, is characterized in that, described bactericide contains quaternary ammonium salt and quaternary alkylphosphonium salt.
3. bactericide as claimed in claim 1 or 2, is characterized in that, described bactericide comprises according to mass percent:
5. as the described bactericide of claim 1-4 any one, it is characterized in that, described quaternary ammonium salt structure as shown in the formula (I):
Wherein, R
1and R
2for replacing or unsubstituted C5 ~ C22 alkyl or replacement or unsubstituted C6 ~ C22 aryl, X is Cl, Br or I independently;
Preferably, R
1and R
2for replacing or unsubstituted C5 ~ C22 alkyl, further preferred independently, R
1and R
2be unsubstituted C6 ~ C20 alkyl independently, particularly preferably, R
1and R
2be unsubstituted C8 ~ C18 alkyl independently;
Preferably, X is Cl or Br;
Particularly preferably, described quaternary ammonium salt structure is as shown in the formula (II):
Wherein, the integer that n is 8 ~ 18, X is Cl or Br.
6. as the described bactericide of claim 1-5 any one, it is characterized in that, described quaternary alkylphosphonium salt structure as shown in the formula (III):
Wherein, R
3, R
4and R
5be replacement or unsubstituted C1 ~ C7 alkyl, replacement or unsubstituted C2 ~ C7 unsaturated alkyl or replacement or unsubstituted phenyl, R independently
6for replacing or unsubstituted C8 ~ C20 alkyl or replacement or unsubstituted C8 ~ C20 aryl, Y is Cl, Br or I;
Preferably, R
3, R
4and R
5for replacing or unsubstituted C2 ~ C7 unsaturated alkyl, further preferred independently, R
3, R
4and R
5be unsubstituted C3 ~ C6 unsaturated alkyl, particularly preferably R independently
3, R
4and R
5for-C
4h
5;
Preferably, R
6for replacing or unsubstituted C8 ~ C20 alkyl, more preferably unsubstituted C10 ~ C18 alkyl, be particularly preferably unsubstituted C11 ~ C16 alkyl;
Preferably, Y is Cl or Br, is particularly preferably Cl;
Particularly preferably, described quaternary alkylphosphonium salt structure is suc as formula shown in (IV):
Wherein, the integer that m is 11 ~ 16.
7. as the described bactericide of claim 1-6 any one, it is characterized in that, described bactericide is composed of the following components according to mass percent:
Wherein, described quaternary ammonium salt structure is as shown in the formula (II):
the integer that n is 8 ~ 18, X is Cl or Br;
8. the purposes as the described bactericide of claim 1-7 any one, is characterized in that, described bactericide is for the oil field extracted water sterilization.
9. the purposes as the described bactericide of claim 1-7 any one, is characterized in that, described bactericide is for the Treatment of Industrial Water field.
10. the using method as the described bactericide of claim 1-7 any one, is characterized in that, described bactericide is more than 30mg/L by the usage amount of possessing watermeter in oil field extracted water.
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