A quaternary phosphonium salt type sterilizing water treatment agent and preparation method thereof

Abstract

The present invention discloses a quaternary phosphonium salt type sterilizing water treatment agent, comprising a sterilizing agent, a flocculant, an adsorbent and deionized water; the structural formula of the sterilizing agent is as follows. The flocculant is selected from one or more of polyaluminium chloride, polyaluminium iron silicate or sodium silicate; the adsorbent is selected from one of calcium chloride or talcum powder; the sterilizing agent is prepared by heating triphenylphosphine and 5-chloro-2-methyl-4-isothiazoline-3-one, and then reacting with 2-chloro-4,6-diamino-1,3,5-triazine. The sterilizing agent contains quaternary phosphonium, quaternary ammonium and triazine structures, sterilizes through the joint action of multiple sterilization mechanisms, and has a high efficiency and broad-spectrum sterilization effect. #imgabs0#

Description

Technical Field

[0001] The invention relates to the field of water treatment technology and environmental engineering technology, and in particular to a quaternary phosphonium salt type sterilizing water treatment agent and a preparation method thereof. Background Art

[0002] The problem of biological corrosion has become a very difficult problem in industrial fields such as oil and gas field production and water treatment systems. Studies have shown that the formation of bacterial biofilm is a necessary condition and direct cause of microbial corrosion (MIC). Therefore, the treatment of biofilm is the key and basis for solving the MIC problem. There are many kinds of microorganisms in industrial circulating cooling water systems and oil and gas field production systems, mainly sulfate-reducing bacteria (SRB), iron bacteria (IB) and saprophytic bacteria (TGB). The growth, metabolism and reproduction of these microorganisms can produce a large amount of mucus-like extracellular polymers (EPS), causing a large amount of biofilm scale to adhere to the inner wall of heat exchange equipment and water injection pipelines, forming slime deposition and scaling. In severe cases, it can directly block the pipeline and cause significant local corrosion in the pipeline facilities. The biofilm is mainly composed of a layer of organic film formed by microorganisms and salts and inorganic ions in the water body. The cell density of the film is 10 7 ~10 10 Colony unit / cm 2 The density of cells in the biofilm fluctuates much higher than that in the suspended state, and can even be 5 to 6 orders of magnitude higher. Currently, highly efficient and broad-spectrum quaternary phosphonium salts are used as the latest bactericides to treat bacteria in sewage.

[0003] Quaternary phosphonium salts are considered to be a new generation of cationic fungicides, which can be used in circulating water systems such as oil field water injection, petrochemical, steel, and power. For example, tetramethylphosphonium chloride is the first generation of quaternary phosphonium salt products used in industrial water treatment, and has been proven to be a multifunctional agent with corrosion inhibition, scale inhibition, and biocidal properties. + THP is a representative new type of quaternary phosphonium salt fungicide, which is particularly effective against SRB. It remains active in high-concentration H2S and underground anaerobic environments. It has the advantages of broad spectrum, high efficiency, no foaming and environmental protection. It has been used as a fungicide in some foreign oil fields. + Salt can form water-soluble complexes with ferrous ions in the presence of ammonium ions, aminophosphates or aminoacetates, and is expected to become an effective scale dissolving agent for iron deposits in acidic oil and gas reservoirs.

[0004] At present, traditional oxidizing and non-oxidizing fungicides are mainly effective against free bacteria in water systems, but have little effect on microorganisms under biofilms, which is mainly due to the limited penetration capacity of traditional fungicides. In addition, due to the long-term use of fungicides alone, microorganisms develop resistance to them, resulting in a gradual increase in the concentration of fungicides and a significant increase in treatment costs. Therefore, there is an urgent need for a quaternary phosphonium salt fungicide that has multiple bactericidal mechanisms, a wide bactericidal range, and high bactericidal efficiency. Summary of the invention

[0005] Purpose of the invention: In view of the defects of the prior art, the purpose of the present invention is to provide a quaternary phosphonium salt type bactericidal water treatment agent with multiple bactericidal mechanisms, high efficiency and broad spectrum and its preparation method.

[0006] Technical solution:

[0007] A quaternary phosphonium salt type sterilizing water treatment agent, comprising a sterilizing agent, a flocculant, an adsorbent and deionized water;

[0008] The bactericide structural formula is as follows:

[0009]

[0010] The bactericide provided by the present invention uses quaternary phosphonium salt as the main body, combines quaternary ammonium group and triazine group, and achieves high-efficiency and broad-spectrum bactericidal effect through multiple bactericidal mechanisms.

[0011] The bactericide provided by the present invention contains a quaternary phosphonium group, which can be adsorbed onto the surface of negatively charged bacteria, diffuse through the cell wall, and combine with the cell plasma membrane to rupture it, and the bacteria die due to the release of the contents. In addition, because the atomic radius of phosphorus is larger than that of nitrogen, the electronegativity of phosphorus is lower, the polarization effect is stronger, and it is easier to adsorb onto the cell membrane, thereby improving the bactericidal ability.

[0012] Furthermore, the flocculant is selected from one or more of polyaluminium chloride, polyaluminium ferrosilicate or sodium silicate.

[0013] The quaternary phosphonium salt type sterilizing water treatment agent provided by the present invention has a strong electrical neutralization effect on colloidal substances in water by adding flocculants, and the hydrolyzate has an excellent bridging adsorption effect on suspended matter in water and a selective adsorption effect on soluble substances. Harmful substances in sewage can be flocculated to improve sterilization efficiency.

[0014] Furthermore, the adsorbent is selected from one of calcium chloride and talc.

[0015] By adding adsorbents, harmful substances can be absorbed, the diffusion time can be reduced, and the sterilization efficiency can be improved.

[0016] Furthermore, based on the total mass being 100%, the mass percentage of each component is:

[0017] Fungicide 1-10%

[0018] Flocculant 10-30%

[0019] Adsorbent 1-5%

[0020] The balance was deionized water.

[0021] Furthermore, based on the total mass being 100%, the mass percentage of each component is:

[0022] Fungicide 3-7%

[0023] Flocculant 15-25%

[0024] Adsorbent 1-3%

[0025] The balance was deionized water.

[0026] The method for preparing any one of the above-mentioned quaternary phosphonium salt type bactericidal water treatment agents comprises the following steps:

[0027] (1) adding triphenylphosphine and 5-chloro-2-methyl-4-isothiazoline-3-one into a reactor, then adding acetone to dissolve, heating, stirring and refluxing for 20-24 hours, cooling to room temperature, filtering, washing and drying to obtain a solid product;

[0028] (2) adding 2-chloro-4,6-diamino-1,3,5-triazine, the solid product of step (1) and acetonitrile to a reactor, heating, stirring and refluxing for 6-10 hours, cooling to room temperature, removing acetonitrile, washing and drying to obtain the fungicide;

[0029] (3) Add a bactericide, a flocculant, an adsorbent and deionized water in a container in order according to their mass percentages, and stir for 30-45 minutes to obtain the quaternary phosphonium salt type bactericidal water treatment agent.

[0030] In step (1), triphenylphosphine is reacted with 5-chloro-2-methyl-4-isothiazolin-3-one to generate a quaternary phosphonium salt and successfully bind isothiazolinone.

[0031] The bactericide provided by the present invention contains quaternary ammonium groups, wherein the positively charged N + It is adsorbed on the cell surface and enters the cell membrane through penetration and diffusion, changing the permeability of the membrane, causing leakage of intracellular substances, inactivation of internal enzymes, and denaturation of proteins, thereby causing the death of the bacteria.

[0032] The fungicide provided by the present invention introduces two different types of characteristic groups, quaternary ammonium salt and quaternary phosphonium salt. + , and P + The more concentrated the positive charge, the better the bactericidal effect.

[0033] The reaction process is as follows:

[0034]

[0035] In step (2), the product of step (1) is reacted with 2-chloro-4,6-diamino-1,3,5-triazine to generate a quaternary ammonium structure and to combine the triazine structure and the amino group to improve the bactericidal effect.

[0036] The bactericide provided by the present invention introduces a triazine group, which is a broad-spectrum pharmacological group with good antibacterial and antiviral activities, is positively charged and hydrophobic, has strong antibacterial activity and low hemolysis, and can effectively inhibit the growth of bacterial biofilms under conditions below the minimum inhibitory concentration.

[0037] The reaction process is as follows:

[0038]

[0039] Furthermore, in the step (1), the mass ratio of triphenylphosphine to 5-chloro-2-methyl-4-isothiazoline-3-one is (25-30):(15-20).

[0040] Furthermore, the temperature of heating, stirring and reflux in step (1) is 55-65°C.

[0041] The mass ratio of 2-chloro-4,6-diamino-1,3,5-triazine in step (2) to the solid product of step (1) is (20-25):(40-50).

[0042] Furthermore, the temperature of heating, stirring and reflux in step (2) is 85-95°C.

[0043] Beneficial effects:

[0044] (1) The bactericide in the quaternary phosphonium salt type bactericidal water treatment agent provided by the present invention is mainly composed of quaternary phosphonium salt, combined with quaternary ammonium group and triazine group, and achieves efficient and broad-spectrum bactericidal effect through multiple bactericidal mechanisms.

[0045] The bactericide provided by the present invention contains a quaternary phosphonium group, which can be adsorbed onto the surface of negatively charged bacteria, diffuse through the cell wall, and combine with the cell plasma membrane to rupture it, and the bacteria die due to the release of the contents. In addition, because the atomic radius of phosphorus is larger than that of nitrogen, the electronegativity of phosphorus is lower, the polarization effect is stronger, and it is easier to adsorb onto the cell membrane, thereby improving the bactericidal ability.

[0046] The bactericide provided by the present invention contains quaternary ammonium groups, wherein the positively charged N +Adsorbed on the cell surface, it penetrates and diffuses into the cell membrane, changes the membrane permeability, causes leakage of intracellular substances, inactivates internal enzymes, and denatures proteins, thus killing the bacteria. The fungicide provided by the present invention introduces two different types of characteristic groups, quaternary ammonium salts and quaternary phosphonium salts, both N + , and P + The more concentrated the positive charge, the better the bactericidal effect.

[0047] The bactericide provided by the present invention introduces a triazine group, which is a broad-spectrum pharmacological group with good antibacterial and antiviral activities, is positively charged and hydrophobic, has strong antibacterial activity and low hemolysis, and can effectively inhibit the growth of bacterial biofilms under conditions below the minimum inhibitory concentration.

[0048] (2) The quaternary phosphonium salt-type sterilizing water treatment agent provided by the present invention assists in the adsorption and treatment of harmful substances in sewage by adding flocculants and adsorbents, thereby improving the sterilization efficiency and sterilization area. DETAILED DESCRIPTION

[0049] The present invention will be described below in conjunction with specific embodiments. It should be noted that the following embodiments are examples of the present invention and are only used to illustrate the present invention, but not to limit the present invention. Other combinations and various modifications within the concept of the present invention may be performed without departing from the spirit or scope of the present invention.

[0050] The commercially available fungicide and algaecide was purchased from Jinan Hongwen Chemical Industry Co., Ltd.; tetraphenylphosphine bromide was A681035 purchased from Shanghai Siyan Biotechnology Co., Ltd.; and the remaining reagents and equipment were conventional reagents and equipment in the technical field.

[0051] Preparation of fungicide-1

[0052] (1) A three-necked round-bottom flask equipped with a thermometer, a stirrer, and a reflux condenser is placed in a water bath, 25 g of triphenylphosphine and 15 g of 5-chloro-2-methyl-4-isothiazoline-3-one are added, and then 200 ml of acetone is added to dissolve, and the mixture is heated to 60° C. and stirred under reflux for reaction for 24 hours, and then naturally cooled to room temperature, filtered, washed, and dried to obtain a solid product;

[0053] (2) placing a three-necked round-bottom flask equipped with a thermometer, a stirrer, and a reflux condenser in a water bath, adding 20 g of 2-chloro-4,6-diamino-1,3,5-triazine, 40 g of the solid product of step (1), and 200 ml of acetonitrile, heating to 90° C., stirring and refluxing for 8 hours, removing the acetonitrile, washing, and vacuum drying to obtain the fungicide-1;

[0054] Preparation of fungicide-2

[0055] The preparation method is basically the same as that of fungicide-1, except that step (2) is not performed and the solid product of step (1) is used as fungicide-2.

[0056] Example 1

[0057] In a container, add bactericide-1, polyaluminium chloride, calcium chloride and deionized water in order according to their mass percentages, and stir for 45 minutes to obtain the quaternary phosphonium salt type bactericidal water treatment agent.

[0058] Taking the total mass as 100%, the mass percentage of each component is:

[0059] Fungicide - 1 3%

[0060] Polyaluminium chloride 15%

[0061] Calcium chloride 3%

[0062] The balance was deionized water.

[0063] Example 2

[0064] The same as Example 1, except that the mass percentage of each component is changed to:

[0065] Fungicide - 1 7%

[0066] Polyaluminium chloride 20%

[0067] Calcium chloride 3%

[0068] The balance was deionized water.

[0069] Example 3

[0070] The same as Example 1, except that the mass percentage of each component is changed to:

[0071] Fungicide - 1 5%

[0072] Polyaluminium chloride 25%

[0073] Calcium chloride 3%

[0074] The balance was deionized water.

[0075] Example 4

[0076] The method is basically the same as Example 1, except that polyaluminium chloride is replaced by polyaluminium ferric silicate; and calcium chloride is replaced by talcum powder.

[0077] Example 5

[0078] The method is basically the same as Example 1, except that polyaluminium chloride is replaced by sodium silicate, and calcium chloride is replaced by talcum powder.

[0079] Comparative Example 1

[0080] Commercially available fungicide and algaecide.

[0081] Comparative Example 2

[0082] The method is basically the same as Example 1, except that the fungicide-1 is replaced by tetraphenylphosphine bromide.

[0083] Comparative Example 3

[0084] The method is basically the same as Example 1, except that fungicide-1 is replaced by fungicide-2.

[0085] Comparative Example 4

[0086] The same as Example 1, except that the mass percentage of each component is changed to:

[0087] Fungicide -1 15%

[0088] Polyaluminium chloride 15%

[0089] Calcium chloride 3%

[0090] The balance was deionized water.

[0091] Comparative Example 5

[0092] The same as Example 1, except that the mass percentage of each component is changed to:

[0093] Fungicide - 1 3%

[0094] Polyaluminium chloride 5%

[0095] Calcium chloride 3%

[0096] The balance was deionized water.

[0097] Performance Testing

[0098] 1. The bactericidal water treatment agents obtained in Examples 1-5 and Comparative Examples 1-5 were tested for their oilfield wastewater bactericidal effects according to the China National Petroleum Corporation corporate standard Q / SY49-2010 "Technical Requirements for Bactericides for Oilfields":

[0099] The sewage is the injection water of an oilfield injection station. The amount of bactericidal water treatment agent added is 40mg / L. Sulfate-reducing bacteria (SRB), iron bacteria (IB) and saprophytic bacteria (TGB) are used as experimental strains after laboratory culture. The bactericidal rate is mainly calculated by testing the bacterial content in the water sample before and after adding the bactericidal water treatment agent. The test results are shown in the following table:

[0100] SRB sterilization rate (%) IB sterilization rate (%) TGB sterilization rate (%) Example 1 99.7 99.5 99.4 Example 2 99.5 97.4 99.7 Example 3 98.1 98.8 98.5 Example 4 99.8 99.6 97.1 Example 5 98.2 99.3 98.5 Comparative Example 1 83.3 79.4 83.3 Comparative Example 2 85.4 84.2 85.4 Comparative Example 3 89.8 87.1 88.7 Comparative Example 4 94.3 94.5 94.9 Comparative Example 5 92.1 92.9 92.5

[0101] According to the test results of Examples 1-5 and Comparative Example 1, the bactericidal water treatment agent provided by the present invention can effectively remove sulfate-reducing bacteria, iron bacteria and saprophytic bacteria in oilfield wastewater compared with commercially available bactericides, with a bactericidal rate of up to 99%, and has extremely strong bactericidal effects on the three types of bacteria.

[0102] According to the test results of Examples 1-5 and Comparative Examples 2 and 3, the bactericidal water treatment agent provided by the present invention has extremely strong bactericidal ability and bactericidal range through the multiple bactericidal mechanisms of the quaternary phosphonium salt and quaternary ammonium and triazine structure of the bactericide.

[0103] 2. The bactericidal water treatment agents obtained in Examples 1-5 and Comparative Examples 1-5 were tested for their bactericidal effects on domestic sewage by the following method:

[0104] The present invention adopts the nutrient broth dilution method for detection, and the antibacterial ability of the antibacterial substance is judged according to the size of the antibacterial zone diameter. The larger the antibacterial zone diameter, the better the antibacterial effect of the surface antibacterial substance. The bacterial species used in the present invention are: Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa, Aspergillus niger, Candida albicans, Aspergillus flavus, Proteus, Bacillus subtilis, and the above microorganisms are prepared into a bacterial suspension using a tryptone soy broth medium for standby use.

[0105] Determination of inhibition zone: Dilute the sterilizing water treatment agent obtained in Examples 1-5 and Comparative Examples 1-5 with water to form a 5% test solution. Use a puncher to make a circular filter paper with a diameter of 6 mm, sterilize and dry for standby use, take 10 mL of test solution respectively, immerse the filter paper in the test solution, soak for 20 minutes, use a sterile coating rod to evenly apply 0.2 mL of bacterial suspension on the surface of the corresponding solid culture medium, wait for 15 minutes after the bacterial solution is completely penetrated, use sterile tweezers to clamp the filter paper with the test solution and the control group and stick it on the bacterial plate, each paper is separated by a certain distance to avoid overlapping of the inhibition zone, set 3 groups of each bacteria, then culture the bacteria for 24 hours, culture the fungi for 48 hours, take out and measure the diameter of the inhibition zone, and take the average value for record.

[0106] 3. The bactericidal water treatment agents obtained in Examples 1-5 and Comparative Examples 1-5 were tested for algae killing effects by the following method:

[0107] The chlorophyll method is used to evaluate the killing effect of the fungicide on algae. The chlorophyll method can measure the growth of algae cells by measuring the content of chlorophyll a. The present invention selects fast-growing Chlorella as the experimental algae species, adds a bactericidal water treatment agent, and the addition amount is 40 mg / L. After 18 hours, the chlorophyll a content of Chlorella is compared with the blank value, thereby measuring the growth of algae cells to evaluate the algaecidal effect of the fungicide.

[0108] The results of tests 2 and 3 are shown in the following table:

[0109]

[0110]

[0111] According to the test results of Examples 1-5 and Comparative Example 1, the bactericidal water treatment agent provided by the present invention has extremely strong bactericidal ability against most types of bacteria, and can effectively kill algae, and has a broad-spectrum and efficient bactericidal ability.

[0112] According to the test results of Examples 1-5 and Comparative Examples 2 and 3, the bactericidal water treatment agent provided by the present invention has extremely strong bactericidal ability and bactericidal range through the multiple bactericidal mechanisms of the quaternary phosphonium salt and quaternary ammonium and triazine structure of the bactericide.

[0113] The above implementation modes are only for illustrating the technical concept and features of the present invention, and their purpose is to enable people familiar with this technology to understand the content of the present invention and implement it, and they cannot be used to limit the protection scope of the present invention. Any equivalent changes or modifications made according to the spirit of the present invention should be included in the protection scope of the present invention.

Claims

1. A quaternary phosphonium salt type sterilizing water treatment agent, characterized in that: Contains bactericide, flocculant, adsorbent and deionized water; The bactericide structural formula is as follows: 。 2. The quaternary phosphonium salt type sterilizing water treatment agent according to claim 1, characterized in that: The flocculant is selected from one or more of polyaluminium chloride, polyaluminium ferrosilicate or sodium silicate.

3. The quaternary phosphonium salt type sterilizing water treatment agent according to claim 1, characterized in that: The adsorbent is selected from one of calcium chloride and talc.

4. The quaternary phosphonium salt type sterilizing water treatment agent according to claim 1, characterized in that: Taking the total mass as 100%, the mass percentage of each component is: Fungicide 1-10% Flocculant 10-30% Adsorbent 1-5% The balance was deionized water.

5. The quaternary phosphonium salt type sterilizing water treatment agent according to claim 4, characterized in that: Taking the total mass as 100%, the mass percentage of each component is: Fungicide 3-7% Flocculant 15-25% Adsorbent 1-3% The balance was deionized water.

6. The method for preparing the quaternary phosphonium salt type bactericidal water treatment agent according to any one of claims 1 to 5, characterized in that: The following steps are involved: (1) Add triphenylphosphine and 5-chloro-2-methyl-4-isothiazoline-3-one into a reactor, then add acetone to dissolve, heat and stir to reflux for 20-24 hours, and then filter, wash and dry to obtain a solid product; (2) Add 2-chloro-4,6-diamino-1,3,5-triazine, the solid product of step (1) and acetonitrile into a reactor, heat, stir and reflux for 6-10 hours, remove the acetonitrile, wash and dry to obtain the fungicide; (3) Add a bactericide, a flocculant, an adsorbent and deionized water in a container in order according to their mass percentages, and stir for 30-45 minutes to obtain the quaternary phosphonium salt type bactericidal water treatment agent.

7. The method for preparing a quaternary phosphonium salt type bactericidal water treatment agent according to claim 6, characterized in that: In the step (1), the mass ratio of triphenylphosphine to 5-chloro-2-methyl-4-isothiazoline-3-one is (25-30): (15-20).

8. The method for preparing a quaternary phosphonium salt type bactericidal water treatment agent according to claim 6, characterized in that: The temperature of heating, stirring and reflux in step (1) is 55-65°C.

9. The method for preparing a quaternary phosphonium salt type bactericidal water treatment agent according to claim 6, characterized in that: The mass ratio of 2-chloro-4,6-diamino-1,3,5-triazine in step (2) to the solid product of step (1) is (20-25):(40-50).

10. The method for preparing a quaternary phosphonium salt type bactericidal water treatment agent according to claim 6, characterized in that: The temperature of heating, stirring and reflux in step (2) is 85-95°C.

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