Quaternary ammonium salts, processes for their preparation and use

Abstract

The application discloses a quaternary ammonium salt, a preparation method and application thereof, and belongs to the field of water treatment agents. The quaternary ammonium salt is a hydroxyl-containing water-soluble polyoxyethylene quaternary ammonium salt cationic surfactant. A non-phosphorus corrosion and scale inhibition bactericide comprises the following components in parts by weight: the aforementioned quaternary ammonium salt 0.1-15 parts, polyaspartic acid or polyaspartic acid salt 0.1-10 parts, gluconate 0.1-5 parts, inorganic zinc salt 0.1-5 parts, citric acid 0.1-5 parts and solvent 60-99.5 parts. The non-phosphorus corrosion and scale inhibition bactericide has good anti-mildew performance, good bactericidal effect and the characteristics of not being easy to bubble, and the types of non-phosphorus agent systems are expanded.

Description

Technical Field

[0001] This invention relates to the field of water treatment technology, specifically to a quaternary ammonium salt, its preparation method, and its application. Background Technology

[0002] Natural gas purification plants bear the important responsibility of desulfurizing and decarbonizing natural gas. The thermal circulation of the process medium is a key link in the entire process. Therefore, the stable operation of the circulating water system is of paramount importance to the safe production of natural gas purification plants. Natural gas purification plants in the Sichuan-Chongqing region generally use open-type circulating cooling water systems, and measures need to be taken to control corrosion, scaling, and sterilization issues during daily operation.

[0003] Adding water treatment agents is currently the most common practice for controlling corrosion, scaling, and bacteria. It is simple to operate, low in cost, and highly effective, with phosphorus-based agents being the most mature. However, with the continuous improvement of agent technology and increasingly stringent environmental regulations, the GB 8978-1996 "Integrated Wastewater Discharge Standard" requires phosphate (as P) ≤0.5 mg / L for Class I discharge. Therefore, phosphate-free water treatment agents have become an inevitable trend.

[0004] In recent years, phosphorus-free chemical systems have also developed rapidly. Currently, carboxylic acid polymers, represented by polyepoxysuccinic acid and polyaspartic acid, have been widely used. Furthermore, CN 112320978A discloses a corrosion-inhibiting, scale-inhibiting, and bactericidal agent, the composition of which contains modified polyaspartic acid, sodium myristoyl glutamate, benzotriazole, and sodium tungstate; CN 110330122A discloses a composite corrosion-inhibiting, scale-inhibiting, and bactericidal agent comprising the following components: a modified nanocellulose quaternary ammonium salt mixture, an oxidized nanocellulose mixture, an alkylamine emulsion, and a betaine-type surfactant; CN114314865A discloses a multifunctional water treatment agent with corrosion inhibition, scale inhibition, and bactericidal properties, prepared by compounding polyglutamic acid, imidazoline, benzyl dimethyl tetradecyl ammonium chloride (BDTAC), and zinc salt with a molecular weight of 15±0.5 kDa.

[0005] Overall, the types and quantities of available phosphorus-free pesticide systems are still relatively small, and there are still certain defects in practical applications, such as the possibility of mold growth, poor bactericidal effect, and severe foaming after prolonged storage. Summary of the Invention

[0006] The technical problem to be solved by this invention is that the types and quantities of existing phosphorus-free reagent systems are still relatively small.

[0007] The first objective of this invention is to provide a quaternary ammonium salt with the structure shown in formula (I). .

[0008] In the formula, the value of m ranges from 0 to 100, the value of n ranges from 0 to 100, both m and n are integers, and m and n are not both 0.

[0009] The quaternary ammonium salt in formula (I) is a cationic surfactant with good bactericidal effect, low surface tension and good water solubility. Therefore, it can be used as a bactericide, which expands the types of phosphorus-free agents.

[0010] A second objective of this invention is to provide a method for preparing the aforementioned quaternary ammonium salt, comprising:

[0011] Triaminonaphthyltriazine was obtained by reverse substitution reaction in the presence of the first initiator and the first catalyst, with 10-20 parts by weight of triazine, 30-40 parts by weight of chloromethylnaphthylamine and 10-15 parts by weight of zinc chloride.

[0012] Triaminonaphthylmethyltriazine and ethylene oxide were reacted in the presence of a second initiator and a second catalyst at a reaction temperature of 150-220°C to obtain the quaternary ammonium salt.

[0013] The triaminonaphthylmethyltriazine is present in parts by weight of 10-15 and the ethylene oxide is present in parts by weight of 80-90.

[0014] A third objective of this invention is to provide a phosphorus corrosion inhibitor, scale inhibitor, and bactericide containing the aforementioned quaternary ammonium salt.

[0015] As one possible design, phosphorus corrosion inhibitors, scale inhibitors, and bactericides also contain polyaspartic acid or polyaspartic acid salts.

[0016] The beneficial effects of this invention are as follows: by using polyaspartic acid or polyaspartic acid salt and quaternary ammonium salt in combination, the resulting phosphorus corrosion inhibitor, scale inhibitor and bactericide has good anti-mildew properties, good bactericidal effect and is not prone to generating bubbles, thus expanding the types of phosphorus-free agent systems. Detailed Implementation

[0017] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the embodiments. The illustrative embodiments and descriptions of this invention are only used to explain this invention and are not intended to limit this invention.

[0018] It should be noted that when a component is referred to as being "fixed to" or "set on" another component, it can be directly on or indirectly on that other component. When a component is referred to as being "connected to" another component, it can be directly connected to or indirectly connected to that other component.

[0019] Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of indicated technical features. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of this invention, "a plurality of" means two or more, unless otherwise explicitly specified. "Several" means one or more, unless otherwise explicitly specified.

[0020] In the description of this invention, it should be noted that, unless otherwise explicitly specified and limited, the terms "installation," "connection," and "linking" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; they can refer to the internal communication of two components or the interaction between two components. Those skilled in the art can understand the specific meaning of the above terms in this invention according to the specific circumstances.

[0021] To address the problem of the limited variety and quantity of existing phosphorus-free reagent systems, this invention provides a quaternary ammonium salt as shown in formula (I).

[0022]

[0023] In the formula, m and n are both integers. The value of m ranges from 0 to 100, for example: 2, 10, 15, 22, 27, 35, 55, 76, 89 and 99, preferably 0 to 45; the value of n ranges from 0 to 100, for example: 2, 10, 15, 22, 27, 35, 55, 76, 89 and 99, preferably 0 to 55. m and n are not both 0.

[0024] The synthetic route of the quaternary ammonium salt shown in formula (I) is as follows: , , .

[0025] The specific synthesis method of the quaternary ammonium salt shown in formula (I) is as follows:

[0026] S1. In the presence of the first initiator and the first catalyst, 10-20 parts by weight of triazine, 30-40 parts by weight of chloromethylnaphthylamine and 10-15 parts by weight of zinc chloride undergo a reverse substitution reaction to obtain triaminonaphthylmethyltriazine;

[0027] S2. Triaminonaphthylmethyltriazine and ethylene oxide are reacted in the presence of a second initiator and a second catalyst at a reaction temperature of 150-220°C to obtain the quaternary ammonium salt;

[0028] The triaminonaphthylmethyltriazine is present in parts by weight of 10-15 and the ethylene oxide is present in parts by weight of 80-90.

[0029] In this invention, step S1 mainly involves a multi-step substitution reaction, in which zinc chloride is used as a catalyst, and the first initiator can be an organic peroxide compound. The amount of initiator is generally 20-25 parts, preferably benzoyl peroxide; the reaction conditions are room temperature and pressure. After the reaction is completed, triaminonaphthylmethyltriazineonium can be purified by extraction and filtration.

[0030] In this invention, in step S2, the second initiator is generally an organic peroxide compound, the second catalyst is generally an aromatic compound, the amount of the second initiator is generally 30-35 parts, preferably benzoyl peroxide; the amount of the second catalyst is generally 20-30 parts, preferably toluene.

[0031] Step S2 can be obtained by two reactions, as follows:

[0032] S21. After the reaction of triaminonaphthylmethyltriazineonium and a portion of ethylene oxide is completed at 150-180℃;

[0033] S22. Then add the second catalyst and the remaining ethylene oxide and react at 200~220℃.

[0034] The entire reaction process takes place in an anaerobic environment, specifically in a closed environment.

[0035] In step S21, ethylene oxide is typically introduced into a sealed environment containing triaminonaphthylmethyltriazine. Before introducing the ethylene oxide, the sealed environment containing the triaminonaphthylmethyltriazine can be evacuated, then heated to 150-220°C, before adding the ethylene oxide, and finally raising the reaction temperature to 150-180°C.

[0036] To prevent the temperature of the reaction system from dropping too quickly after the addition of ethylene oxide, it can be heated to a certain temperature, such as 55~70℃, before adding ethylene oxide.

[0037] To avoid excessive pressure in the sealed environment, which could compromise the safety of the synthesis process, ethylene oxide can be continuously introduced until the required amount is reached. During this continuous introduction, the pressure in the sealed environment should be maintained at 0.2–0.3 MPa. Once the required amount of ethylene oxide has been added, and the pressure in the sealed environment reaches a negative pressure, the reaction is complete, yielding tris[(N,N)-hydroxyethylnaphthylmethyl]-triazineonium.

[0038] In step S22, before adding the remaining ethylene oxide, the tris[(N,N)-hydroxyethylnaphthylmethyl]-triazineonium obtained in step S21 can be cooled to 70-80°C while the catalyst is added simultaneously. When the pressure in the sealed environment becomes negative, it indicates that the reaction process is complete, and the product can be discharged after cooling. The temperature after cooling is generally 70-80°C.

[0039] The present invention also discloses a phosphorus corrosion inhibitor, scale inhibitor, and bactericide, comprising a quaternary ammonium salt as shown in formula (I).

[0040] In this invention, the phosphorus corrosion inhibitor, scale inhibitor, and bactericide may also include polyaspartic acid or polyaspartic acid salt. By compounding quaternary ammonium salt with polyaspartic acid or polyaspartic acid salt, it not only has a good bactericidal effect, but also has stable performance and is not prone to generating bubbles.

[0041] In this invention, the phosphorus corrosion inhibitor, scale inhibitor, and bactericide may further include gluconate, inorganic zinc salt, citric acid, and solvent, with the following specific mass parts: 0.1-15 parts of the aforementioned quaternary ammonium salt, 0.1-10 parts of polyaspartic acid or polyaspartic acid salt, 0.1-5 parts of gluconate, 0.1-5 parts of inorganic zinc salt, 0.1-5 parts of citric acid, and 60-99.5 parts of solvent.

[0042] The preferred phosphorus-free corrosion inhibitor, scale inhibitor, and bactericide comprises the following components in parts by weight: 5-10 parts of the aforementioned quaternary ammonium salt, 2-5 parts of polyaspartic acid or polyaspartic acid salt, 1-3 parts of gluconate, 2-4 parts of inorganic zinc salt, 2-3 parts of citric acid, and 19-84 parts of solvent. Example

[0043] (1) At room temperature and pressure, 35g of triazine, 90g of chloromethylnaphthylamine and 30g of zinc chloride are placed in a five-necked flask for reaction. After multiple substitution reactions, triaminonaphthylmethyltriazine can be obtained by extraction and filtration.

[0044] (2) In a dry reaction vessel equipped with a stirrer, a vacuum-pressure meter, a vacuum connector, a thermometer tube, and an EO inlet tube (EO is ethylene oxide), add the product triaminonaphthylmethyltriazine obtained in (1). Vacuum the vessel to remove air, start stirring and heat to 150~160℃. When the ethylene oxide water bath temperature rises to 55~60℃, open the EO inlet tube valve and slowly introduce a metered amount of EO gas into the vessel, maintaining the pressure inside the vessel at 0.2~0.3 MPa, and keeping the temperature inside the vessel at 170~200℃. When a negative pressure appears inside the vessel, it indicates that the reaction process is complete. Cool to 70~80℃ and discharge to obtain tri[(N,N)-hydroxyethylnaphthylmethyl]-triazine.

[0045] (3) Using this as a starting agent and adding a catalyst, additional EO gas is introduced under the above process conditions, and the temperature inside the reactor is maintained at around 200℃. When a negative pressure appears inside the reactor, it indicates that the reaction process is complete. Cool to 70~80℃ and discharge to obtain product 1. Example

[0046] (1) At room temperature and pressure, 45g of triazine, 110g of chloromethylnaphthylamine and 40g of zinc chloride were placed in a five-necked flask for reaction. After multiple substitution reactions, the triaminonaphthylmethyltriazine was obtained by extraction and filtration.

[0047] (2) In a dry reaction vessel equipped with a stirrer, a vacuum-pressure connector, a vacuum tube, a thermometer tube, and an EO tube (EO is ethylene oxide), add the product triaminonaphthylmethyltriazineon obtained in (1). Evacuate the vessel to remove air, start stirring and heat to 180~210℃. When the temperature of the ethylene oxide water bath rises to 60~65℃, open the EO tube valve and slowly introduce a metered amount of EO gas into the vessel, maintaining the pressure inside the vessel at 0.2~0.3 MPa, and keeping the temperature inside the vessel at 150~180℃. When a negative pressure appears inside the vessel, it indicates that the reaction process is complete. Cool to 70~80℃ and discharge to obtain tri[(N,N)-hydroxyethylnaphthylmethyl]-triazineon.

[0048] (3) Using this as a starting agent and adding a catalyst, additional EO gas is introduced under the above process conditions, and the temperature inside the reactor is maintained at around 210℃. When a negative pressure appears inside the reactor, it indicates that the reaction process is complete. Cool to 70~80℃ and discharge to obtain product 2. Example

[0049] (1) At room temperature and pressure, 55g of triazine, 130g of chloromethylnaphthylamine and 50g of zinc chloride were placed in a five-necked flask for reaction. After multiple substitution reactions, the triaminonaphthylmethyltriazine was obtained by extraction and filtration.

[0050] (2) In a dry reaction vessel equipped with a stirrer, a vacuum-pressure meter, a vacuum connector, a thermometer tube, and an EO inlet tube (EO is ethylene oxide), add the product triaminonaphthylmethyltriazineon obtained in (1). Evacuate the vessel to remove air, start stirring and heat to 190~220℃. When the ethylene oxide water bath temperature rises to 65~70℃, open the EO inlet tube valve and slowly introduce a metered amount of EO gas into the vessel, maintaining the pressure inside the vessel at 0.2~0.3 MPa, and keeping the temperature inside the vessel at 150~180℃. When a negative pressure appears inside the vessel, it indicates that the reaction process is complete. Cool to 70~80℃ and discharge to obtain tri[(N,N)-hydroxyethylnaphthylmethyl]-triazineon.

[0051] (3) Using this as a starting agent and adding a catalyst, additional EO gas is introduced under the above process conditions, and the temperature inside the reactor is maintained at around 220°C. When a negative pressure appears inside the reactor, it indicates that the reaction process is complete. Cool to 70~80°C and discharge to obtain product 3. Example

[0052] This embodiment uses the hydroxyl-containing water-soluble polyoxyethylene quaternary ammonium salt cationic surfactant obtained in Example 1 as an example to formulate a phosphorus-free corrosion and scale inhibitor.

[0053] Five parts by weight of a hydroxyl-containing water-soluble polyoxyethylene quaternary ammonium salt cationic surfactant, five parts of polyaspartic acid, two parts of sodium gluconate, two parts of zinc sulfate, two parts of citric acid, and eighty-four parts of water were placed in a container and mixed evenly to obtain a phosphorus-free corrosion and scale inhibitor. Example

[0054] This embodiment uses the hydroxyl-containing water-soluble polyoxyethylene quaternary ammonium salt cationic surfactant obtained in Example 2 as an example to formulate a phosphorus-free corrosion and scale inhibitor.

[0055] Eight parts by weight of a hydroxyl-containing water-soluble polyoxyethylene quaternary ammonium salt cationic surfactant, two parts of polyaspartic acid, three parts of sodium gluconate, three parts of zinc sulfate, three parts of citric acid, and 79 parts of water were placed in a container and mixed evenly to obtain a phosphorus-free corrosion and scale inhibitor. Example

[0056] This embodiment uses the hydroxyl-containing water-soluble polyoxyethylene quaternary ammonium salt cationic surfactant obtained in Example 3 as an example to formulate a phosphorus-free corrosion and scale inhibitor.

[0057] Ten parts by weight of a water-soluble polyoxyethylene quaternary ammonium salt cationic surfactant containing hydroxyl groups, two parts of polyaspartic acid, one part of sodium gluconate, four parts of zinc sulfate, two parts of citric acid, and eighty-one parts of water were placed in a container and mixed evenly to obtain a phosphorus-free corrosion and scale inhibitor.

[0058] Test

[0059] Experimental Example 1

[0060] Experimental solution: Standard water as recommended in the standard

[0061] Pharmaceuticals: Examples 4, 5, and 6 above.

[0062] Evaluation method: Refer to GB / T18175-2014 "Determination of Corrosion Inhibition Performance of Water Treatment Agents"

[0063] Experimental temperature: 45℃

[0064] Drug concentration: 80 ppm

[0065] Experiment duration: 72 hours

[0066] The test method employed an RCC-Ⅱ type rotating plate corrosion tester. The test material was 20# carbon steel with a surface area of ​​28 cm², and the plate rotation speed was 75 rpm, exposed naturally to air (without other continuous ventilation devices). The corrosion test was conducted in a 2L beaker with two test plates installed simultaneously, and the average value was taken as the result.

[0067] Table 1. Measurement of corrosion rate

[0068]

[0069] As shown in Table 1, the phosphorus-free corrosion inhibitor, scale inhibitor, and bactericide prepared by this invention has good corrosion inhibition performance.

[0070] Experiment Example 2

[0071] Experimental solution: Standard test solution (water quality)

[0072] Experimental reagents: Examples 4, 5, and 6 mentioned above.

[0073] Evaluation method: Refer to GB / T16632-2008 "Determination of Scale Inhibition Performance of Water Treatment Agents"

[0074] Experimental temperature: 80℃

[0075] Drug concentration: 80 ppm

[0076] Experiment duration: 10 hours

[0077] The static scale inhibition method was used for evaluation, and the calcium ion content was determined by EDTA titration.

[0078] Table 2 Evaluation of scale inhibition rate

[0079]

[0080] As shown in Table 2, the phosphorus-free corrosion inhibitor, scale inhibitor, and bactericide prepared by this invention has good scale inhibition performance, reaching over 92%.

[0081] Experimental Example 3

[0082] Experimental solution: reinjection water from a gas field in southern Sichuan

[0083] Experimental reagents: Examples 4, 5, and 6 above, dodecyl dimethyl benzyl ammonium chloride, and tetramethyl phosphate sulfate.

[0084] Evaluation methods: SY / T5329 "Water Quality Indicators and Analytical Methods for Injection Water in Clastic Rock Reservoirs", SY / T5890 "Performance Evaluation Methods for Bactericides"

[0085] Experimental temperature: 40℃

[0086] Drug concentration: 100 mg / L

[0087] Incubation time: 168 hours

[0088] Number of sulfate-reducing bacteria (SRB): 20 × 10 3 cells / mL

[0089] Number of saprophytic bacteria (TGB): 70 × 10⁻⁶ 4 cells / mL

[0090] Iron bacteria (FB) count: 70 × 10 4 cells / mL

[0091] The test results are as follows:

[0092] Table 3. Sterilization Efficacy Test

[0093]

[0094] As shown in Table 3, the phosphorus-free corrosion and scale inhibitor prepared by this invention has good compatibility with the gas field water system and a better overall bactericidal effect than the other two bactericides in gas field water treatment.

[0095] Experiment Example 4

[0096] Experimental solution: tap water

[0097] Experimental reagents: 4, 5, and 6 mentioned above, the three examples, sample 1, and sample 2.

[0098] Evaluation method: 200ml liquid, 11000 rpm, stir for 1 min, and test the foam volume after 10 seconds.

[0099] Experimental temperature: room temperature

[0100] Drug concentration: 1%

[0101] Table 4 Evaluation of Foaming Performance

[0102]

[0103] As shown in Table 4, the phosphorus-free corrosion inhibitor, scale inhibitor, and bactericide prepared by this invention has low surface tension and is not prone to foaming.

[0104] Experimental Example 5

[0105] Experimental reagents: Examples 4, 5, and 6 above, three examples, Sample 1, and Sample 2;

[0106] Evaluation method: The test reagent was left exposed to air.

[0107] Experimental temperature: 30℃

[0108] Experiment duration: 30 days

[0109] Table 5 Evaluation of Anti-mildew Performance

[0110]

[0111] As shown in Table 5, the phosphorus-free corrosion and scale inhibitors prepared in Examples 4-6 exhibited good anti-mold properties, and no mold growth occurred after 30 days of storage. The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of this invention. It should be understood that the above descriptions are merely specific embodiments of this invention and are not intended to limit the scope of protection of this invention. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of this invention should be included within the scope of protection of this invention.

Claims

1. The quaternary ammonium salt shown in formula (I), (I) In the formula, the value of m ranges from 0 to 100, the value of n ranges from 0 to 100, both m and n are integers, and m and n are not both 0.

2. The quaternary ammonium salt according to claim 1, characterized in that, The value of m ranges from 0 to 45; the value of n ranges from 0 to 55, and m and n are not both 0.

3. The method for preparing the quaternary ammonium salt according to claim 1 or 2, characterized in that, The preparation method includes: Triaminonaphthyltriazine was obtained by reverse substitution reaction in the presence of the first initiator and the first catalyst, with 10-20 parts by weight of triazine, 30-40 parts by weight of chloromethylnaphthylamine and 10-15 parts by weight of zinc chloride. 10-15 parts of triaminonaphthylmethyltriazine and 80-90 parts of ethylene oxide were reacted in the presence of a second initiator and a second catalyst at a reaction temperature of 150-220°C to obtain the quaternary ammonium salt.

4. The preparation method according to claim 3, characterized in that, The reaction between triaminonaphthylmethyltriazine and ethylene oxide proceeds in two steps, specifically including: After the triaminonaphthylmethyltriazine and a portion of ethylene oxide are reacted at 150-180°C, a second catalyst and the remaining ethylene oxide are added and reacted at 200-220°C.

5. The preparation method according to claim 4, characterized in that, After the reaction of triaminonaphthylmethyltriazine and part of ethylene oxide is completed, the mixture is cooled to 70-80°C, and then a second catalyst and the remaining ethylene oxide are added and reacted at 200-220°C.

6. The preparation method according to claim 4, characterized in that, The reaction of triaminonaphthylmethyltriazine with a portion of ethylene oxide is as follows: Ethylene oxide is added to triaminonaphthylmethyltriazine, and the reaction ends when the pressure in the reaction vessel becomes negative.

7. The preparation method according to claim 4, characterized in that, Before mixing ethylene oxide and triaminonaphthyltriazine, the temperature of ethylene oxide is 55~70℃.

8. A phosphorus-free corrosion inhibitor, scale inhibitor, and bactericide, comprising the quaternary ammonium salt as described in claim 1 or 2.

9. The phosphorus-free corrosion inhibitor, scale inhibitor, and bactericide according to claim 8, characterized in that, The components include the following parts by weight: 0.1 to 15 parts of the quaternary ammonium salt according to claim 1 or 2; 0.1 to 10 parts of polyaspartic acid or polyaspartic acid salt; 0.1 to 5 parts of gluconate; Inorganic zinc salt 0.1–5 parts; Citric acid 0.1–5 parts; Solvent 60~99.5 parts.

10. The phosphorus-free corrosion inhibitor, scale inhibitor, and bactericide according to claim 9, characterized in that, The components include the following parts by weight: 5-10 parts of the quaternary ammonium salt according to claim 1 or 2; 2-5 parts of polyaspartic acid or polyaspartic acid salt; 1-3 parts gluconate; 2-4 parts of inorganic zinc salt; Citric acid 2-3 parts; Solvent: 19-84 parts.

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