CN114426323A - Oil field polymer bactericidal flocculant and preparation method and application thereof - Google Patents
Oil field polymer bactericidal flocculant and preparation method and application thereof Download PDFInfo
- Publication number
- CN114426323A CN114426323A CN202010997606.2A CN202010997606A CN114426323A CN 114426323 A CN114426323 A CN 114426323A CN 202010997606 A CN202010997606 A CN 202010997606A CN 114426323 A CN114426323 A CN 114426323A
- Authority
- CN
- China
- Prior art keywords
- flocculant
- bactericidal
- mole
- amount
- cosolvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/10—Solids, e.g. total solids [TS], total suspended solids [TSS] or volatile solids [VS]
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention belongs to the technical field of sewage treatment, and particularly relates to an oil field polymer bactericidal flocculant as well as a preparation method and application thereof. The preparation method comprises the following steps: in the presence of a cosolvent A and alkali liquor, performing a first-step substitution reaction on fatty secondary amine and chlorinated alkene to generate tertiary amine, and performing a second-step substitution reaction on the tertiary amine and sodium chloroalkyl benzene sulfonate to generate quaternary ammonium salt; and (3) carrying out polymerization reaction on the quaternary ammonium salt generated in the step (2) in the presence of a cosolvent B, a buffer salt and an initiator to obtain the bactericidal flocculant. The chloroolefin and the chloroalkylbenzene sulfonic acid sodium are respectively used in an amount of 0.7-1.3 parts by mole and 0.8-1.2 parts by mole based on 1 part by mole of the secondary aliphatic amine. The bactericidal flocculant has the characteristics of simple synthesis process, low cost and no secondary pollution, and has the function of combining sterilization and flocculation. The sterilization rate of the sulfate reducing bacteria reaches more than 99 percent, and the removal rate of suspended matters in the oily sewage reaches more than 80 percent.
Description
Technical Field
The invention belongs to the technical field of sewage treatment, and particularly relates to an oil field polymer bactericidal flocculant as well as a preparation method and application thereof.
Background
The method is characterized in that the stratum energy is gradually reduced in the middle and later stages of oil field development, the primary oil recovery technology cannot meet the production requirement, the existing oil recovery technology mainly comprises secondary oil recovery and tertiary oil recovery, a large amount of water is required to be injected into the stratum to supplement the stratum deficit energy, and the injected water is recycled, so that the components in the water are more and more complex, various bacteria are easily bred, and the bacteria mainly comprise sulfate reducing bacteria, saprophytic bacteria and iron bacteria. Among them, sulfate reducing bacteria have the greatest influence on oil field production, and can cause metal corrosion, formation blockage and medicament performance reduction. These all cause significant economic losses to the oil field production operation.
The produced water of the oil field contains higher suspended matters, the components are more complex, and the treatment difficulty is more and more large. Too high suspended solids can cause the water injection pressure of the oil field to increase, the energy consumption to increase, and the formation can be damaged, so that the recovery efficiency is seriously influenced. Thus, oil fields have strict standards for suspended matter in the quality of water being injected.
CN104488874A discloses a compound bactericide for an oil field water injection system. The composite bactericide for the oilfield water injection system is characterized by comprising, by weight, 0-80% of a water solution containing 45-55% of benzalkonium chloride, 10-20% of an ethanol solution containing 25-35% of cetylpyridinium bromide and 10-15% of a xylene solution containing 18-22% of tetrachloroisophthalonitrile. Has the advantages of simple components, convenient preparation, high sterilization rate and the like. However, the compound component contains a large amount of cetylpyridinium bromide, and the cetylpyridinium bromide has increased toxicity, and can cause secondary pollution and environmental damage after being used.
CN103478164A discloses an oilfield sewage bactericide and a preparation method thereof, wherein the oilfield sewage bactericide is prepared by mixing nano titanium dioxide powder, a cross-linking agent, a surfactant and an oxidant according to the following mass percentages: 10-15% of nano titanium dioxide powder, 0.5-2% of cross-linking agent, 5-10% of surfactant and 5-10% of oxidant, and the bactericide can be deposited on the pipe wall, corner and other positions along with liquid flow, and has the characteristics of lasting drug effect, no corrosion to the pipeline, long dosing period and the like. However, the compound components have large content of titanium dioxide heavy metals, which can cause environmental damage, and the cost is high, so that the compound is difficult to popularize on a large scale.
At present, the most common flocculant of oilfield sewage is a PAC and PAM composite medicament. When in use, the water needs to be added twice, the operation is complex, and different water needs different compound concentrations, thereby increasing the difficulty of field operation. The functions of each medicament in the above technology are single, and the same medicament only has sterilization or flocculation effect.
Disclosure of Invention
The invention aims to provide an oil field polymer bactericidal flocculant as well as a preparation method and application thereof aiming at the defects of the prior art, and the bactericidal flocculant has the characteristics of simple synthesis process, low cost and no secondary pollution and has the function of combining sterilization and flocculation. The sterilization rate of the sulfate reducing bacteria reaches more than 99 percent, and the removal rate of suspended matters in the oily sewage reaches more than 80 percent.
Therefore, in order to achieve the above objects, in one aspect, the present invention provides a method for preparing an oilfield polymer bactericidal flocculant, the method comprising the following steps:
(1) in the presence of a cosolvent A and alkali liquor, performing a first-step substitution reaction on aliphatic secondary amine and chlorinated olefin to generate tertiary amine.
(2) And (2) in the presence of an organic solvent, carrying out a second-step substitution reaction on the tertiary amine generated in the step (1) and chloroalkyl benzene sulfonate to generate the quaternary ammonium salt.
(3) And (3) carrying out polymerization reaction on the quaternary ammonium salt generated in the step (2) in the presence of a cosolvent B, a buffer salt and an initiator to obtain a crude product of the bactericidal flocculant.
(4) And (4) dropwise adding a reducing agent into the bactericidal flocculant mixture obtained through the polymerization reaction in the step (3), removing excessive initiator, and cooling to room temperature to obtain the bactericidal flocculant.
The chloroolefin and the chloroalkylbenzene sulfonic acid sodium are respectively used in an amount of 0.7-1.3 parts by mole and 0.8-1.2 parts by mole based on 1 part by mole of the secondary aliphatic amine.
In another aspect, the invention provides a bactericidal flocculant prepared by the above method, wherein the molecular formula of the bactericidal flocculant is as follows:
wherein R is1And R2Each independently is C1-C4 alkyl, R3And R4Is C1-C3 alkylene.
The molecular weight of the bactericidal flocculant is 1000000-5000000.
In a third aspect, the invention provides the application of the bactericidal flocculant in the treatment of oily sewage in an oil field. The specific application is not particularly required, and can be a conventional application mode in the field, and the detailed description is not repeated.
The invention provides an oil field polymer bactericidal flocculant for oil field sewage sterilization and flocculation, which belongs to quaternary ammonium salt, can adsorb negatively charged bacteria, gather on cell walls, generate a chamber resistance effect, cause the bacteria to be inhibited and die, and can adsorb on the surfaces of bacterial cells, thereby changing the conductivity, surface tension, solubility and the like of cell membranes, deteriorating proteins, inhibiting or stimulating the activity of enzyme, controlling a plasma membrane damaging the permeability of the cells, and killing sulfate reducing bacteria; the bactericidal flocculant molecule contains sulfonic acid groups, has surface activity, and can directly act on the surface of bacteria through emulsified oil, so that the defect that the emulsified oil forms a protective layer on the surface of the bacteria to reduce the drug effect is overcome; the sterilization flocculant contains polar groups such as amino groups on the molecules, the surface of the sterilization flocculant is charged, when the sterilization flocculant is added into oily sewage, electrostatic attraction effect is generated between colloid particles in the sewage and the sterilization flocculant until the dosage of the sterilization flocculant reaches a certain degree, the surface charge of the colloid particles is completely neutralized, electrostatic repulsion force disappears, and the particles can approach each other through Brownian motion, so that the colloid particles are destabilized and form larger flocs to sink, and the purpose of separating mud from water is achieved; the bactericidal flocculant is a high molecular polymer, has large molecular weight and long molecular chain length, can adsorb a plurality of colloidal particles onto active groups of a molecular chain, plays a role of bridging, can mutually twine macromolecules adsorbing a plurality of particles to generate flocs with larger size, collects residual fine particles in some solutions in the process of slowly sinking into flocs, plays a role of net catching, and carries the fine particles to sink together. Therefore, the flocculation flocculant has a composite effect of multiple functions.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the bactericidal flocculant has the advantages of wide raw material source, simple synthesis process, strong adaptability and small dosage, and can meet the requirement of oil field development;
(2) the sterilization flocculant does not contain inorganic components, does not produce pollution and is environment-friendly;
(3) the bactericidal flocculant of the invention has the functions of sterilization and flocculation, the bactericidal rate on sulfate reducing bacteria reaches 99 percent, and the removal rate on suspended matters in oily sewage reaches 80 percent.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
According to a first aspect of the invention, the invention provides a preparation method of an oilfield polymer bactericidal flocculant, which comprises the following steps:
(1) in the presence of a cosolvent A and alkali liquor, performing a first-step substitution reaction on aliphatic secondary amine and chlorinated olefin to generate tertiary amine.
(2) And (2) in the presence of an organic solvent, carrying out a second-step substitution reaction on the tertiary amine generated in the step (1) and chloroalkyl benzene sulfonate to generate the quaternary ammonium salt.
(3) And (3) carrying out polymerization reaction on the quaternary ammonium salt generated in the step (2) in the presence of a cosolvent B, a buffer salt and an initiator to obtain a crude product of the bactericidal flocculant.
(4) And (4) dropwise adding a reducing agent into the bactericidal flocculant mixture obtained through the polymerization reaction in the step (3), removing excessive initiator, and cooling to room temperature to obtain the bactericidal flocculant.
The chloroolefin and the chloroalkylbenzene sulfonic acid sodium are respectively used in an amount of 0.7-1.3 parts by mole and 0.8-1.2 parts by mole based on 1 part by mole of the secondary aliphatic amine.
In the present invention, it is preferable that the chloroolefin and the sodium chloroalkylbenzenesulfonate be used in amounts of 0.8 to 1.2 parts by mole and 0.9 to 1.1 parts by mole, respectively, based on 1 part by mole of the secondary aliphatic amine. More preferably, the chloroolefin and the sodium chloroalkylbenzenesulfonate are used in amounts of 0.9 to 1.1 parts by mole and 0.95 to 1.05 parts by mole, respectively, based on 1 part by mole of the secondary aliphatic amine.
Preferably, in the step (1), the cosolvent a is one of ethylene glycol, ethanol and propanol, and is more preferably ethylene glycol or ethanol. The cosolvent a is used in an amount of 1 to 10 mol parts, more preferably 2 to 8 mol parts, based on 1 mol part of the secondary aliphatic amine.
Preferably, in the step (1), the alkali solution is one of an aqueous solution of sodium hydroxide, sodium bicarbonate and potassium hydroxide, and more preferably an aqueous solution of sodium hydroxide or sodium bicarbonate. The mass concentration of the alkali liquor is 5-10%. The alkali solution is used in an amount of 0.1 to 1.1 parts by mole based on 1 part by mole of the secondary aliphatic amine.
Preferably, in step (1), the conditions of the first-step substitution reaction include a temperature of 40 to 70 ℃ for 1 to 10 hours, a stirring speed of 100 to 300rpm, more preferably a temperature of 50 to 60 ℃ for 2 to 5 hours, and a stirring speed of 200 to 300 rpm.
Preferably, in the step (1), the chlorinated olefin and the alkali liquor are added dropwise separately and simultaneously, and the dropwise adding time is the same and is 1-8 h.
According to a more specific preferred embodiment, the step (1) further comprises the steps of separating the produced tertiary amine, dehydrating the dehydrating agent, and subjecting the tertiary amine to oil bath distillation under reduced pressure.
The dehydrating agent is one of solid sodium hydroxide or solid calcium oxide, and the temperature of oil bath distillation is 200-250 ℃.
In the present invention, preferably, in step (2), the organic solvent is one of ethanol, propanol and butanol, and more preferably ethanol or propanol. The organic solvent is used in an amount of 1 to 10 parts by mole, more preferably 2 to 8 parts by mole, based on 1 part by mole of the secondary aliphatic amine.
Preferably, in step (2), the conditions of the second-step substitution reaction include a temperature of 40 to 70 ℃, a time of 0.5 to 2 hours, and a stirring speed of 40 to 120 rpm. More preferably at a temperature of 50-60 deg.C for 1-1.5h, and at a stirring speed of 50-100 rpm.
According to a more specific preferred embodiment, the step (2) further comprises a step of subjecting the resulting quaternary ammonium salt to liquid separation and oil bath vacuum distillation treatment. The temperature of the oil bath reduced pressure distillation is 200-220 ℃.
In the invention, preferably, in the step (3), the cosolvent B is one of OP-10, sodium dodecyl sulfate and an MS-1 aqueous solution, and more preferably OP-10 or sodium dodecyl sulfate. The cosolvent B is used in an amount of 0.2 to 1 molar part, more preferably 0.4 to 0.6 molar part, based on 1 molar part of the secondary aliphatic amine. The mass fraction of the water solution of the cosolvent B is 5-20%, and more preferably 10-15%.
Preferably, in the step (3), the buffer salt is one of 20% ammonia water, sodium phosphate and potassium phosphate, and more preferably 20% ammonia water or sodium phosphate. The buffer salt is used in an amount of 0.2 to 1 molar part, more preferably 0.4 to 0.8 molar part, based on 1 molar part of the secondary fatty amine.
Preferably, in the step (3), the initiator is one of hydrogen peroxide, hydrogen peroxide and sodium peroxide, and more preferably hydrogen peroxide or hydrogen peroxide. The initiator is used in an amount of 0.01 to 0.2 molar parts, more preferably 0.05 to 0.1 molar parts, based on 1 molar part of the secondary aliphatic amine.
In the present invention, preferably, in the step (3), the polymerization conditions include a temperature of 30 to 80 ℃, a time of 5 to 20 hours, and a stirring speed of 100 to 500 rpm.
Preferably, in step (3), the polymerization conditions comprise two stages which are sequentially carried out, and the reaction conditions of the first stage comprise: the temperature is 30-50 ℃, the time is 3-15h, and the stirring speed is 100-300 rpm; the reaction conditions of the second stage include: the temperature is 60-80 ℃, the time is 2-5h, and the stirring speed is 400-500 rpm.
In the present invention, preferably, in the step (4), the reducing agent is sodium bisulfite or sodium hydrosulfite, and more preferably, sodium bisulfite. The reducing agent is used in an amount of 0.02 to 0.1 molar parts, more preferably 0.03 to 0.05 molar parts, based on 1 molar part of the secondary aliphatic amine.
Preferably, the specific step of removing the excessive initiator in the step (4) includes dropping the reducing agent and sampling until the test paper shows no blue color, and then cooling to room temperature by using circulating water.
In a second aspect, the invention provides a bactericidal flocculant prepared by the method, wherein the molecular formula of the bactericidal flocculant is as follows:
wherein R is1And R2Each independently is C1-C4Alkyl of R3And R4Is C1-C3An alkylene group of (a).
In the present invention, said C1-C4Examples of the alkyl group of (a) may include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl.
In the present invention, the alkylene group may be linear or branched. Said C is1-C3Examples of alkylene groups of (a) may include, but are not limited to: methylene, ethylene, n-propylene, isopropylene. The alkylene group refers to a residue of an alkane which has been deprived of two hydrogen atoms, which may be two hydrogen atoms on the same carbon atom or two hydrogen atoms on different carbon atoms, and which may be linear or branched, for example, the ethylene group may be-CH2 CH2-or-CH (CH)3)-。
In the present invention, R1Preferably methyl or ethyl, R2Preferably isopropyl or isobutyl.
Preferably, the molecular weight of the bactericidal flocculant is 1000000-5000000, more preferably 2000000-3000000.
In a third aspect, the invention provides the application of the bactericidal flocculant in the treatment of oily sewage in an oil field. The specific application is not particularly required, and can be a conventional application mode in the field, and the detailed description is not repeated.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
The present invention will be further described with reference to specific examples.
In the present invention, the apparatus or equipment used is a conventional apparatus or equipment known in the art, and is commercially available.
In the following examples and comparative examples, the reagents used are all chemically pure reagents from commercial sources, unless otherwise specified.
The performance test of the product is carried out by adopting the following method:
the molecular weight test method refers to GB/T31816-2015 gel chromatography for determining molecular weight and distribution of water treatment agent polymer
The method for testing the removal rate of suspended matters refers to the general technical conditions of flocculating agent for treating conventional produced water in Q/SH 10201356-2016 oilfield
The sterilization rate of the sulfate reducing bacteria refers to SY/T5329-2012 clastic rock oil reservoir water injection quality index and analysis method and SY/T5757-2010 oilfield injection water bactericide general technical conditions
Example 1 Synthesis of bactericidal flocculant A
(1) In the presence of a cosolvent A and alkali liquor, 1 mol of aliphatic secondary amine and 0.7 mol of chlorinated olefin undergo a first-step substitution reaction to generate tertiary amine. And carrying out liquid separation, solid sodium hydroxide dehydration and 200 ℃ oil bath distillation on the generated tertiary amine to obtain the tertiary amine with high purity.
The cosolvent A is propanol, and the using amount is 1 mol part.
The alkali liquor is sodium bicarbonate aqueous solution, the dosage is 0.1 molar part, and the mass concentration is 5%.
The conditions of the first-step substitution reaction include a temperature of 40 ℃, a time of 5 hours and a stirring speed of 100 rpm.
The chlorinated olefin and the alkali liquor are added in a separated and simultaneous manner, and the adding time is the same and is 1 h.
(2) And (2) in the presence of an organic solvent, carrying out a second-step substitution reaction on the tertiary amine generated in the step (1) and 1.2 mol of chloroalkylbenzene sodium sulfonate to generate the quaternary ammonium salt. And carrying out liquid separation and oil bath reduced pressure distillation at 200 ℃ on the generated quaternary ammonium salt to obtain the quaternary ammonium salt with high purity.
The organic solvent is ethanol, and the using amount is 1 molar part.
The conditions of the second substitution reaction include a temperature of 70 ℃, a time of 2 hours, and a stirring speed of 40 rpm.
(3) And (3) carrying out polymerization reaction on the quaternary ammonium salt generated in the step (2) in the presence of a cosolvent B, a buffer salt and an initiator to obtain a crude product of the bactericidal flocculant.
The cosolvent B is OP-10 aqueous solution, the using amount is 0.2 mol, and the mass fraction is 5%.
The buffer salt is sodium phosphate, and the dosage is 0.2 mol.
The initiator is sodium peroxide, and the dosage is 0.01 mol.
The polymerization reaction conditions comprise two stages which are sequentially carried out, and the reaction conditions of the first stage comprise: the temperature is 30 ℃, the time is 3h, and the stirring speed is 100 rpm; the reaction conditions of the second stage include: the temperature was 80 ℃ and the time 2h, the stirring speed 400 rpm.
(4) And (3) dropwise adding 0.02 mol of reducer sodium hydrosulfite into the bactericidal flocculant mixture obtained by the polymerization reaction in the step (3), simultaneously dropwise adding and sampling until the starch potassium iodide test paper shows no blue color, and then cooling to room temperature by using circulating water to obtain the bactericidal flocculant A.
Example 2 Synthesis of bactericidal flocculant B
(1) In the presence of a cosolvent A and alkali liquor, 1 mol of aliphatic secondary amine and 0.8 mol of chlorinated olefin undergo a first-step substitution reaction to generate tertiary amine. And carrying out liquid separation, solid calcium oxide dehydration and oil bath distillation at 210 ℃ on the generated tertiary amine to obtain the tertiary amine with high purity.
The cosolvent A is ethanol, and the using amount is 2 mol parts.
The alkali liquor is potassium hydroxide aqueous solution, the using amount is 0.3 molar parts, and the mass concentration is 6%.
The conditions of the first-step substitution reaction include a temperature of 45 ℃, a time of 4 hours, and a stirring speed of 150 rpm.
The chlorinated olefin and the alkali liquor are added in a separated and simultaneous manner, and the adding time is the same and is 3 hours.
(2) And (2) in the presence of an organic solvent, carrying out a second-step substitution reaction on the tertiary amine generated in the step (1) and 1.1 mol of chloroalkylbenzene sodium sulfonate to generate the quaternary ammonium salt. And carrying out liquid separation and 210 ℃ oil bath reduced pressure distillation on the generated quaternary ammonium salt to obtain the quaternary ammonium salt with high purity.
The organic solvent is propanol, and the using amount is 3 mol parts.
The conditions for the second substitution reaction included a temperature of 60 ℃ for 1.5 hours and a stirring speed of 60 rpm.
(3) And (3) carrying out polymerization reaction on the quaternary ammonium salt generated in the step (2) in the presence of a cosolvent B, a buffer salt and an initiator to obtain a crude product of the bactericidal flocculant.
The cosolvent B is a sodium dodecyl sulfate aqueous solution, the using amount is 0.4 mol, and the mass fraction is 10%.
The buffer salt was potassium phosphate in an amount of 0.4 mole.
The initiator is hydrogen peroxide, and the dosage is 0.04 mol.
The polymerization reaction conditions comprise two stages which are sequentially carried out, and the reaction conditions of the first stage comprise: the temperature is 40 ℃, the time is 6h, and the stirring speed is 150 rpm; the reaction conditions of the second stage include: the temperature was 75 ℃ and the time 3h, the stirring speed 450 rpm.
(4) And (3) dropwise adding 0.04 mol of reducing agent sodium bisulfite into the bactericidal flocculant mixture obtained by the polymerization reaction in the step (3), simultaneously dropwise adding and sampling until the starch potassium iodide test paper shows no blue color, and then cooling to room temperature by using circulating water to obtain the bactericidal flocculant B.
Example 3 Synthesis of bactericidal flocculant C
(1) In the presence of a cosolvent A and alkali liquor, 1 mol of aliphatic secondary amine and 1.0 mol of chlorinated olefin undergo a first-step substitution reaction to generate tertiary amine. And carrying out liquid separation, solid sodium hydroxide dehydration and 220 ℃ oil bath distillation on the generated tertiary amine to obtain the tertiary amine with high purity.
The cosolvent A is ethylene glycol, and the using amount is 5 mol parts.
The alkali liquor is sodium hydroxide aqueous solution, the using amount is 0.6 molar parts, and the mass concentration is 7%.
The conditions of the first-step substitution reaction include a temperature of 50 ℃, a time of 3 hours and a stirring speed of 200 rpm.
The chlorinated olefin and the alkali liquor are added in a separated and simultaneous manner, and the adding time is the same and is 5 hours.
(2) And (2) in the presence of an organic solvent, carrying out a second-step substitution reaction on the tertiary amine generated in the step (1) and 1.0 mol of chloroalkylbenzene sodium sulfonate to generate the quaternary ammonium salt. And carrying out liquid separation and oil bath reduced pressure distillation at 220 ℃ on the generated quaternary ammonium salt to obtain the quaternary ammonium salt with high purity.
The organic solvent is ethanol, and the using amount is 5 molar parts.
The conditions for the second substitution reaction included a temperature of 55 deg.C, a time of 1.5h, and a stirring speed of 80 rpm.
(3) And (3) carrying out polymerization reaction on the quaternary ammonium salt generated in the step (2) in the presence of a cosolvent B, a buffer salt and an initiator to obtain a crude product of the bactericidal flocculant.
The cosolvent B is an MS-1 aqueous solution, the using amount is 0.6 mol, and the mass fraction is 15%. The buffer salt is 20% ammonia water, and the dosage is 0.6 mol.
The initiator is hydrogen peroxide, and the dosage is 0.08 mol.
The polymerization reaction conditions comprise two stages which are sequentially carried out, and the reaction conditions of the first stage comprise: the temperature is 50 ℃, the time is 9h, and the stirring speed is 200 rpm; the reaction conditions of the second stage include: the temperature was 70 ℃ and the time 3h, the stirring speed 450 rpm.
(4) And (3) dropwise adding 0.06 mol of reducing agent sodium bisulfite into the bactericidal flocculant mixture obtained by the polymerization reaction in the step (3), simultaneously dropwise adding and sampling until the starch potassium iodide test paper shows no blue color, and then cooling to room temperature by using circulating water to obtain the bactericidal flocculant C.
Example 4 Synthesis of bactericidal flocculant D
(1) In the presence of a cosolvent A and alkali liquor, 1 mol of aliphatic secondary amine and 1.1 mol of chlorinated olefin undergo a first-step substitution reaction to generate tertiary amine. And carrying out liquid separation, solid sodium hydroxide dehydration and 230 ℃ oil bath distillation on the generated tertiary amine to obtain the tertiary amine with high purity.
The cosolvent A is ethanol, and the using amount is 8 molar parts.
The alkali liquor is potassium hydroxide aqueous solution, the using amount is 0.9 molar part, and the mass concentration is 8%.
The conditions of the first-step substitution reaction include a temperature of 60 ℃, a time of 3 hours and a stirring speed of 250 rpm.
The chlorinated olefin and the alkali liquor are added in a separated and simultaneous manner, and the adding time is the same and is 7 hours.
(2) And (2) in the presence of an organic solvent, carrying out a second-step substitution reaction on the tertiary amine generated in the step (1) and 0.9 mol of chloroalkylbenzene sodium sulfonate to generate the quaternary ammonium salt. And carrying out liquid separation and 230 ℃ oil bath reduced pressure distillation on the generated quaternary ammonium salt to obtain the quaternary ammonium salt with high purity.
The organic solvent is propanol, and the using amount is 8 mol parts.
The conditions for the second substitution reaction included a temperature of 50 ℃ for 1.0 hour and a stirring speed of 100 rpm.
(3) And (3) carrying out polymerization reaction on the quaternary ammonium salt generated in the step (2) in the presence of a cosolvent B, a buffer salt and an initiator to obtain a crude product of the bactericidal flocculant.
The cosolvent B is OP-10 aqueous solution, the using amount is 0.8 mol, and the mass fraction is 15%. The buffer salt is potassium phosphate, and the dosage is 0.8 mol.
The initiator is hydrogen peroxide, and the dosage is 0.15 mol.
The polymerization reaction conditions comprise two stages which are sequentially carried out, and the reaction conditions of the first stage comprise: the temperature is 60 ℃, the time is 12h, and the stirring speed is 250 rpm; the reaction conditions of the second stage include: the temperature was 65 ℃ and the time 4h, the stirring speed 450 rpm.
(4) And (3) dropwise adding 0.08 mol of reducing agent sodium bisulfite into the bactericidal flocculant mixture obtained by the polymerization reaction in the step (3), simultaneously dropwise adding and sampling until the starch potassium iodide test paper shows no blue color, and then cooling to room temperature by using circulating water to obtain the bactericidal flocculant D.
Example 5 Synthesis of bactericidal flocculant E
(1) In the presence of a cosolvent A and alkali liquor, 1 mol of aliphatic secondary amine and 1.3 mol of chlorinated olefin undergo a first-step substitution reaction to generate tertiary amine. And carrying out liquid separation, solid calcium oxide dehydration and oil bath distillation at 250 ℃ on the generated tertiary amine to obtain the tertiary amine with high purity.
The cosolvent A is propanol, and the using amount is 10 mol parts.
The alkali liquor is sodium hydroxide aqueous solution, the using amount is 1.1 molar parts, and the mass concentration is 10%.
The conditions of the first-step substitution reaction include a temperature of 70 ℃, a time of 2h and a stirring speed of 300 rpm.
The chlorinated olefin and the alkali liquor are added in a separated and simultaneous manner, and the adding time is the same and is 8 hours.
(2) And (2) in the presence of an organic solvent, carrying out a second-step substitution reaction on the tertiary amine generated in the step (1) and 0.8 mol of chloroalkylbenzene sodium sulfonate to generate the quaternary ammonium salt. And carrying out liquid separation and oil bath reduced pressure distillation at 250 ℃ on the generated quaternary ammonium salt to obtain the quaternary ammonium salt with high purity.
The organic solvent is ethanol, and the using amount is 10 molar parts.
The conditions for the second substitution reaction included a temperature of 40 deg.C, a time of 0.5h, and a stirring speed of 120 rpm.
(3) And (3) carrying out polymerization reaction on the quaternary ammonium salt generated in the step (2) in the presence of a cosolvent B, a buffer salt and an initiator to obtain a crude product of the bactericidal flocculant.
The cosolvent B is a sodium dodecyl sulfate aqueous solution, the using amount is 1.0 mol, and the mass fraction is 20%.
The buffer salt is sodium phosphate, and the dosage is 1.0 mol.
The initiator is hydrogen peroxide, and the dosage is 0.2 mol.
The polymerization reaction conditions comprise two stages which are sequentially carried out, and the reaction conditions of the first stage comprise: the temperature is 80 ℃, the time is 15h, and the stirring speed is 300 rpm; the reaction conditions of the second stage include: the temperature was 60 ℃ and the time 5h, the stirring speed 500 rpm.
(4) And (3) dropwise adding 0.1 mol of reducer sodium hydrosulfite into the bactericidal flocculant mixture obtained by the polymerization reaction in the step (3), simultaneously dropwise adding and sampling until the starch potassium iodide test paper shows no blue color, and then cooling to room temperature by using circulating water to obtain the bactericidal flocculant E.
Example 6 in-situ application of bactericidal flocculant A
United station B3The incoming water is produced water of an oil well of an oil production plant of a victory oil field, and the treatment scale is 3000m3The content of sulfate reducing bacteria in the produced water is 60/ml, the content of suspended matters is 100mg/L, and the bactericidal flocculant A is utilized to the combination station B2The produced water is sterilized and flocculated, the adding amount of the sterilizing flocculating agent A is 30kg/d, the content of sulfate reducing bacteria is reduced to 0.6/ml after treatment, the sterilizing rate is 99 percent, the sterilizing effect is good, and the process requirement is met. The content of the treated suspended matters is reduced to 15mg/L, the removal rate of the suspended matters is 85 percent, the flocculation effect is good, and the process requirement is met.
Example 7 in-situ application of bactericidal flocculant B
United station L3The incoming water is the produced water of an oil well of a certain oil production plant of the victory oil field, and the treatment scale is 2000m3D, the sulfate reducing bacteria content in the produced water is 250/ml, the suspended matter content is 80mg/L, and the bactericidal flocculant B is utilized to the combination station L3The produced water is sterilized and flocculated, the adding amount of the sterilizing flocculating agent B is 20kg/d, the content of sulfate reducing bacteria is reduced to 0.6 per ml after treatment, the sterilizing rate is 99.8 percent, the sterilizing effect is good, and the purpose of achieving the aim of industrial production is achievedThe process requirement is met. The content of the treated suspended matters is reduced to 10mg/L, the removal rate of the suspended matters is 88 percent, the flocculation effect is good, and the process requirement is met.
Example 8 in situ application of Fungicide flocculant C
United station G12The incoming water is produced water of an oil well of a certain oil production plant of the victory oil field, and the treatment scale is 4000m3D, the content of sulfate reducing bacteria in the produced water is 60/ml, the content of suspended matters is 80mg/L, and the sterilizing flocculant C provided by the invention is utilized for the combination station G12The produced water is sterilized and flocculated, the adding amount of the sterilizing flocculating agent C is 40kg/d, the content of sulfate reducing bacteria is reduced to 0/ml after treatment, the sterilizing rate is 100%, the sterilizing effect is good, and the process requirement is met. The content of the treated suspended matters is reduced to 5mg/L, the removal rate of the suspended matters is 94 percent, the flocculation effect is good, and the process requirement is met.
Example 9 in-situ application of bactericidal flocculant D
United station C4The incoming water is produced water of an oil well of an oil production plant of a victory oil field, and the treatment scale is 3000m3D, the content of sulfate reducing bacteria in the produced water is 25/ml, the content of suspended matters is 60mg/L, and the bactericidal flocculant D is utilized to the combination station C4The produced water is sterilized and flocculated, the adding amount of the sterilizing flocculating agent D is 30kg/D, the content of sulfate reducing bacteria is reduced to 0/ml after treatment, the sterilizing rate is 100%, the sterilizing effect is good, and the process requirement is met. The content of the treated suspended matters is reduced to 8mg/L, the removal rate of the suspended matters is 87 percent, the flocculation effect is good, and the process requirement is met.
Example 10 in-situ application of bactericidal flocculant E
United station L5The incoming water is the produced water of an oil well of a certain oil production plant of the victory oil field, and the treatment scale is 2000m3D, the content of sulfate reducing bacteria in the produced water is 60/ml, the content of suspended matters is 110mg/L, and the sterilization flocculant E of the invention is utilized to the combination station L5The produced water is sterilized and flocculated, the adding amount of the sterilizing flocculating agent E is 20kg/d, the content of sulfate reducing bacteria is reduced to 0.6 per ml after treatment, the sterilizing rate is 99 percent, the sterilizing effect is good, and the process requirement is met. Reduction of suspended matter content after treatmentThe concentration is as low as 20mg/L, the removal rate of suspended matters is 82 percent, the flocculation effect is good, and the process requirement is met.
Comparative example 1
United station B3The incoming water is produced water of an oil well of an oil production plant of a victory oil field, and the treatment scale is 3000m3The sulfate reducing bacteria content in the produced water is 60/ml, the suspended matter content is 100mg/L, and the conventional bactericide 1227 is utilized to treat the united station B2The produced water is sterilized, the adding amount of the bactericide 1227 is 30kg/d, the content of sulfate reducing bacteria is reduced to 15/ml after treatment, the sterilization rate is 75%, and the sterilization effect is general. Utilizing conventional flocculating agents PAC and PAM to combine the station B3The produced water is flocculated, the adding amount of PAC is 60kg/d, the adding amount of PAM is 30kg/d, the content of suspended substances after treatment is reduced to 25mg/L, the removal rate of the suspended substances is 75 percent, and the flocculation effect is general.
Comparative example 2
United station L3The incoming water is the produced water of an oil well of a certain oil production plant of the victory oil field, and the treatment scale is 2000m3The sulfate reducing bacteria content in the produced water is 250/ml, the suspended matter content is 80mg/L, and the conventional bactericide 1227 is utilized to treat the united station L3The produced water is sterilized, the adding amount of the bactericide 1227 is 20kg/d, the content of sulfate reducing bacteria is reduced to 45/ml after treatment, the sterilization rate is 82%, and the sterilization effect is general. Utilizing conventional flocculating agents PAC and PAM to combine the station B3The produced water is flocculated, the adding amount of PAC is 40kg/d, the adding amount of PAM is 20kg/d, the content of suspended substances after treatment is reduced to 24mg/L, the removal rate of the suspended substances is 70 percent, and the flocculation effect is general.
TABLE 1 germicidal flocculant A, B, C, D, E Performance index test results
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (21)
1. The preparation method of the oil field polymer bactericidal flocculant is characterized by comprising the following steps of:
(1) in the presence of a cosolvent A and alkali liquor, performing a first-step substitution reaction on aliphatic secondary amine and chlorinated olefin to generate tertiary amine;
(2) in the presence of an organic solvent, carrying out a second-step substitution reaction on the tertiary amine generated in the step (1) and chloroalkyl benzene sulfonate to generate a quaternary ammonium salt;
(3) in the presence of a cosolvent B, buffer salt and an initiator, performing polymerization reaction on the quaternary ammonium salt generated in the step (2) to obtain a crude product of the bactericidal flocculant;
(4) and (4) dropwise adding a reducing agent into the bactericidal flocculant mixture obtained through the polymerization reaction in the step (3), removing excessive initiator, and cooling to room temperature to obtain the bactericidal flocculant.
The chloroolefin and the chloroalkylbenzene sulfonic acid sodium are respectively used in an amount of 0.7-1.3 parts by mole and 0.8-1.2 parts by mole based on 1 part by mole of the secondary aliphatic amine.
2. The method according to claim 1, wherein the chlorinated alkene and the sodium chloroalkylbenzenesulfonate are used in an amount of 0.8 to 1.2 parts by mole and 0.9 to 1.1 parts by mole, respectively, based on 1 part by mole of the secondary aliphatic amine.
3. The preparation method according to claim 1, wherein the cosolvent A is one of ethylene glycol, ethanol and propanol; the cosolvent a is used in an amount of 1 to 10 parts by mole based on 1 part by mole of the secondary aliphatic amine.
4. The preparation method according to claim 3, wherein the cosolvent A is ethylene glycol or ethanol, and is used in an amount of 2 to 8 molar parts based on 1 molar part of the secondary aliphatic amine.
5. The process according to claim 1, wherein the first-step substitution reaction is carried out at a temperature of 40 to 70 ℃ for 1 to 10 hours at a stirring speed of 100 to 300 rpm.
6. The production method according to claim 1, wherein the step (1) further comprises the steps of separating the produced tertiary amine, dehydrating the dehydrating agent, and subjecting the tertiary amine to oil bath vacuum distillation; the dehydrating agent is one of solid sodium hydroxide or solid calcium oxide, and the temperature of oil bath distillation is 200-250 ℃.
7. The method according to claim 1, wherein the organic solvent is one of ethanol, propanol and butanol, and is used in an amount of 1 to 10 parts by mole based on 1 part by mole of the secondary aliphatic amine.
8. The process according to claim 1, wherein the conditions for the second substitution reaction include a temperature of 40 to 70 ℃ and a time of 0.5 to 2 hours, and a stirring speed of 40 to 120 rpm.
9. The production method according to claim 1, wherein the step (2) further comprises a step of subjecting the produced quaternary ammonium salt to liquid separation and oil bath vacuum distillation treatment at a temperature of 200 to 220 ℃.
10. The preparation method of claim 1, wherein the cosolvent B is one of OP-10, sodium dodecyl sulfate and an aqueous solution of MS-1, and is used in an amount of 0.2 to 1 molar part based on 1 molar part of the secondary aliphatic amine.
11. The method according to claim 1, wherein the buffer salt is one of 20% ammonia water, sodium phosphate and potassium phosphate, and is used in an amount of 0.2 to 1 mol part based on 1 mol part of the secondary aliphatic amine.
12. The preparation method of claim 1, wherein the initiator is one of hydrogen peroxide, hydrogen peroxide and sodium peroxide, and the amount of the initiator is 0.01 to 0.2 mole part based on 1 mole part of the secondary fatty amine.
13. The process according to claim 1, wherein in the step (3), the polymerization conditions include a temperature of 30 to 80 ℃, a time of 5 to 20 hours, and a stirring speed of 100 to 500 rpm.
14. The process according to claim 13, wherein in the step (3), the polymerization conditions comprise two stages which are sequentially carried out, and the reaction conditions of the first stage comprise: the temperature is 30-50 ℃, the time is 3-15h, and the stirring speed is 100-300 rpm; the reaction conditions of the second stage include: the temperature is 60-80 ℃, the time is 2-5h, and the stirring speed is 400-500 rpm.
15. The method according to claim 1, wherein the reducing agent is sodium bisulfite or sodium hydrosulfite, and is used in an amount of 0.02 to 0.1 parts by mole based on 1 part by mole of the secondary aliphatic amine.
16. The method according to claim 1, wherein in the step (4), the step of removing the excess initiator comprises the steps of dropping the reducing agent while sampling to a starch potassium iodide test strip until the test strip shows no blue color, and then cooling to room temperature by using circulating water.
17. The bactericidal flocculant prepared by the preparation method according to any one of claims 1 to 16.
18. The bactericidal flocculant of claim 17, wherein the bactericidal flocculant has the following formula:
wherein R is1And R2Each independently is C1-C4Alkyl of R3And R4Is C1-C3An alkylene group of (a).
19. The bactericidal flocculant of claim 18, wherein R1Is methyl or ethyl, R2Is isopropyl or isobutyl.
20. The bactericidal flocculant of claim 18, having a molecular weight of 1000000-5000000.
21. Use of a bactericidal flocculant according to any one of claims 17 to 20 in the treatment of oily sewage in an oil field.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010997606.2A CN114426323B (en) | 2020-09-21 | 2020-09-21 | Oil field polymer sterilization flocculant and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010997606.2A CN114426323B (en) | 2020-09-21 | 2020-09-21 | Oil field polymer sterilization flocculant and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114426323A true CN114426323A (en) | 2022-05-03 |
| CN114426323B CN114426323B (en) | 2022-11-04 |
Family
ID=81310102
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010997606.2A Active CN114426323B (en) | 2020-09-21 | 2020-09-21 | Oil field polymer sterilization flocculant and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114426323B (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8411499D0 (en) * | 1984-05-04 | 1984-06-13 | Procter & Gamble | Non-caking detergent |
| KR20030012692A (en) * | 2001-08-03 | 2003-02-12 | 주식회사 엘지생활건강 | Surfactant system |
| CN1648142A (en) * | 2004-12-29 | 2005-08-03 | 华东理工大学 | Copolymer for diesel low temperature flow promoter and its preparing method |
| CN101525291A (en) * | 2009-04-03 | 2009-09-09 | 浙江工业大学 | Green asymmetric synthesis method of chiral bicyclics compound |
| CN101857588A (en) * | 2010-06-08 | 2010-10-13 | 东南大学 | 4-aromatic aminoquinazoline derivative and purpose thereof |
| CN102229674A (en) * | 2011-04-12 | 2011-11-02 | 淮海工学院 | Multifunctional chelating cellulose and application thereof |
| CN107235529A (en) * | 2017-06-27 | 2017-10-10 | 中国石油化工股份有限公司 | A kind of degreaser handled for oil-contaminated water of oil field and preparation method thereof |
| CN108069625A (en) * | 2017-12-25 | 2018-05-25 | 安徽同力新材料有限公司 | A kind of glass fiber yarn high efficiency infiltration agent |
| CN109153749A (en) * | 2016-05-31 | 2019-01-04 | 三菱化学株式会社 | Polymer, the manufacturing method of polymer and high polymer coagulant |
| CN110240549A (en) * | 2019-07-10 | 2019-09-17 | 南阳师范学院 | A kind of amine alkoxy chalcone compound and its preparation method and application |
-
2020
- 2020-09-21 CN CN202010997606.2A patent/CN114426323B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8411499D0 (en) * | 1984-05-04 | 1984-06-13 | Procter & Gamble | Non-caking detergent |
| KR20030012692A (en) * | 2001-08-03 | 2003-02-12 | 주식회사 엘지생활건강 | Surfactant system |
| CN1648142A (en) * | 2004-12-29 | 2005-08-03 | 华东理工大学 | Copolymer for diesel low temperature flow promoter and its preparing method |
| CN101525291A (en) * | 2009-04-03 | 2009-09-09 | 浙江工业大学 | Green asymmetric synthesis method of chiral bicyclics compound |
| CN101857588A (en) * | 2010-06-08 | 2010-10-13 | 东南大学 | 4-aromatic aminoquinazoline derivative and purpose thereof |
| CN102229674A (en) * | 2011-04-12 | 2011-11-02 | 淮海工学院 | Multifunctional chelating cellulose and application thereof |
| CN109153749A (en) * | 2016-05-31 | 2019-01-04 | 三菱化学株式会社 | Polymer, the manufacturing method of polymer and high polymer coagulant |
| CN107235529A (en) * | 2017-06-27 | 2017-10-10 | 中国石油化工股份有限公司 | A kind of degreaser handled for oil-contaminated water of oil field and preparation method thereof |
| CN108069625A (en) * | 2017-12-25 | 2018-05-25 | 安徽同力新材料有限公司 | A kind of glass fiber yarn high efficiency infiltration agent |
| CN110240549A (en) * | 2019-07-10 | 2019-09-17 | 南阳师范学院 | A kind of amine alkoxy chalcone compound and its preparation method and application |
Non-Patent Citations (6)
| Title |
|---|
| ALBANO, CARMEN ET AL.: ""Gamma-radiation effects in pp stabilized with different additives"", 《REVISTA DE LA FACULTAD DE INGENIERÍA UNIVERSIDAD CENTRAL DE VENEZUELA》 * |
| GAUTAM, SURYA PRAKASH ET AL.: ""An Alternative Approach for Acetylation of Amine Terminated Polyamidoamine (PAMAM) Dendrimer"", 《ARS PHARMACEUTICA (INTERNET)》 * |
| SUN, PF ET AL.: ""Preparation of a new-style composite containing a key bioflocculant produced by Pseudomonas aeruginosa ZJU1 and its flocculating effect on harmful algal blooms"", 《JOURNAL OF HAZARDOUS MATERIAL》 * |
| 丁铮: ""中和-氧化-混凝法联合处理油田酸化废液"", 《环境工程学报》 * |
| 张建枚等: ""PAMAM树形分子季铵盐的合成及其性能研究"", 《2008中国水处理技术研讨会暨第28届年会论文集》 * |
| 李传宪等: ""油溶性双亲分子对草桥稠油缔合结构与流动性的影响"", 《高效化学工程学报》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114426323B (en) | 2022-11-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105076201B (en) | A kind of Compositional type oil-field flooding bactericide | |
| Zhao et al. | Microbial mineralization of struvite: salinity effect and its implication for phosphorus removal and recovery | |
| WO2012145949A1 (en) | Microorganism for displacing oil and composite oil-displacement agent comprising such microorganism | |
| CN108041035A (en) | A kind of dication epoxy type fungicide and preparation method thereof | |
| CN108651462B (en) | Chitosan zwitter-ion bactericide and preparation method and application thereof | |
| CN114426323B (en) | Oil field polymer sterilization flocculant and preparation method and application thereof | |
| CN105254821A (en) | Terpolymer, multifunctional water treatment agent containing same and preparation method of multifunctional water treatment agent | |
| CN107488166A (en) | It is a kind of to be used for bactericide of sulfate reducing bacteria and preparation method thereof in oilfield sewage | |
| CN114907403B (en) | Double quaternary phosphonium salt bactericide and synthetic method thereof | |
| CN107324466A (en) | Method is prepared in situ in a kind of river course water treatment coagulant | |
| CN117362520A (en) | Flocculant for sewage treatment and preparation method thereof | |
| CN108033578A (en) | A kind of Treated sewage reusing low-phosphorus antiincrustation corrosion inhibitor and preparation method thereof | |
| CN107593703A (en) | For the bactericide and its preparation method of oil field water treatment system and application | |
| CN116948088A (en) | Sewage degreasing agent and preparation method and application thereof | |
| CN115073517A (en) | Quaternary phosphonium quaternary ammonium salt bactericide and synthetic method thereof | |
| CN108541706B (en) | Application of star-shaped compound carrying dense charges as bactericide | |
| CN104285955A (en) | Germicide and algicide composition and preparation method of germicide and algicide composition | |
| CN103598186A (en) | Biradical metronidazole modified bis-quaternary ammonium salt sterilizing agent and preparation method thereof | |
| CN104496141A (en) | Method for promotion of biodegradation of perfluorochemicals in sludge | |
| CN112167259B (en) | Oxidizing bactericide, preparation method and application thereof | |
| CN118206530A (en) | Oily sewage bactericide and synthetic method thereof | |
| CN113973819B (en) | High-efficiency bactericide and preparation method thereof | |
| CN108541707B (en) | Application of star-shaped multi-cation-based compound as bactericide | |
| CN205222900U (en) | 2 - chloroethyl propyl ether effluent treatment plant | |
| CN104396953A (en) | Novel efficient germicide and algicide and preparation process thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |