JP2014201697A - Contamination prevention agent and contamination prevention method for ammonia water treatment facilities - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a contamination prevention agent for ammonia treatment facilities, which can be added to the ammonia treatment facilities while operating the ammonia treatment facilities without introducing a new device, and which exhibits both effects of functioning as an emulsion breaker, and contamination dispersion, namely device contamination cleaning and nozzle clogging prevention, and to provide a contamination prevention method of the ammonia treatment facilities using the same.SOLUTION: There is provided a contamination prevention agent for ammonia water treatment facilities, including at least one kind selected from a higher fatty acid amine ethylene oxide addition product, and a higher fatty acid amide ethylene oxide addition product, as a contamination prevention component for solving the above-mentioned problem.

Description

  The present invention relates to an antifouling agent and an antifouling method for an aqueous water (ammonia water) treatment facility. More specifically, the present invention relates to the prevention of stains in a water treatment facility containing a specific surfactant that exhibits both the effect of emulsion breaker and stain dispersion in a water treatment facility such as a coke plant as a stain prevention component. The present invention relates to an agent and a stain prevention method using the same.

High-temperature gas (Coke Oven Gas, hereinafter referred to as “COG”) generated from coke ovens such as steelworks is used to separate and recover components and heat through various treatments, product tar, Used as renewable energy.
The tar component, which is the main component of COG, is condensed when the COG is cooled to 80 to 85 ° C. by the aqueous flushing in the dry main of the aquatic treatment facility, and is collected in the tar decanter together with the aqueous water. Light tar components are recovered from the primary cooler, tar extractor, and electrostatic precipitator and transferred to a tar decanter.

The tar component recovered in the tar decanter is separated into aqueous water, tar and tar sludge by staying, and the aqueous water is circulated for COG cooling (aqueous water flushing). The tar sludge accumulated in is scraped out every few hours by a discharge scraper.
The tar transferred from the tar decanter contains some sludge and moisture, and the moisture is removed by a centrifuge or the like (see FIG. 1).
The tar usually contains about 3 to 20% by weight of water, and the water contains a small amount of ammonium salt. Therefore, the moisture in tar causes corrosion of the apparatus, bumping phenomenon during distillation, and inhibition of rectification due to foaming, and also shows high vapor pressure, making pressure control difficult and increasing fuel consumption. Therefore, it is necessary to remove the moisture in the tar as much as possible.

  That is, tar is usually temporarily stored in a tank, and at that time, a tar emulsion layer exists in the tank for a long time. For this reason, when tar containing a high moisture content tar emulsion is supplied to the dehydration facility in the first step of the tar distillation plant, dehydration becomes insufficient due to insufficient capacity of the dehydration facility. Will occur, and the device cannot be operated. For this reason, the tar normally supplied to the tar distillation plant is controlled at a maximum water content of 4% by weight. As a measure for controlling the moisture content, a surfactant (emulsion breaker) is added to tar to promote separation of the tar emulsion into a tar phase and an aqueous phase, thereby reducing moisture in the tar.

In order to solve the above problems, measures for cleaning the apparatus and preventing nozzle clogging have been proposed.
For example, in Japanese Patent No. 4964283 (Patent Document 1), there is a method for treating surplus water that passes through a separation plate centrifuge, and in Japanese Patent Application Laid-Open No. 2008-255172 (Patent Document 2), a boiling point of 100 ° C. A method for reducing water from a tar or a tar emulsion is disclosed in which the following ammonia compound is removed to phase-separate and remove water.
JP 2002-97494 A (Patent Document 3) discloses a chemical plant cleaning method including a step of introducing an aromatic hydrocarbon having a specific carbon number and distillation properties as a cleaning agent and immersing insoluble dirt. It is disclosed.
However, the above-described method has a problem that it is necessary to introduce a new device or stop all or part of equipment for cleaning the device.

Japanese Patent No. 4964283 JP 2008-255172 A JP 2002-97494 A

  Therefore, the present invention has been made in view of the above-described problems and current state of the prior art, and an emulsion breaker and a soil dispersion, that is, a device that can be added while operating the equipment without introducing a new device. An object of the present invention is to provide an antifouling agent for a water-safe treatment facility that exhibits both the effect of cleaning the dirt and preventing nozzle clogging, and a method for preventing dirt using the same.

In order to solve the above-mentioned problems, the inventors of the present invention focused on a specific emulsion breaker (surfactant) that exhibits the effects of cleaning the apparatus and preventing nozzle clogging. The inventors have found that amine ethylene oxide adducts and higher aliphatic amide ethylene oxide adducts have particularly excellent effects, and have completed the present invention.
Until now, various surfactants have been used as stain cleaning components in the technical field, but higher aliphatic amine ethylene oxide adducts and higher aliphatic amide ethylene oxide adducts have a particularly excellent effect. It was not known.

  Thus, according to the present invention, the antifouling agent for water-safety treatment equipment contains at least one selected from a higher aliphatic amine ethylene oxide adduct and a higher fatty acid amide ethylene oxide adduct as an antifouling component. Is provided.

  Further, according to the present invention, the antifouling agent is added so that the antifouling component is in a ratio of 10 to 500 g / ton with respect to tar in the water for safe water treatment equipment. There is provided a method for preventing contamination of a water treatment facility, wherein the tar emulsion is separated into a tar phase and an aqueous phase and the contamination of the water treatment facility is prevented.

According to the present invention, an emulsion breaker that can be added while the equipment is in operation without introducing a new device, and a water-resistant solution that exhibits both the effects of soil dispersion, that is, cleaning of the device and preventing nozzle clogging. An antifouling agent for a processing facility and an antifouling method using the same can be provided.
That is, according to the present invention, tar or light oil or the like does not adhere or accumulate in the stripper tower or downstream equipment / equipment in a water treatment facility such as a coke plant. Adhesion can be prevented without stopping and nozzle blockage can be prevented.

In addition, the antifouling agent for the water-safety treatment facility of the present invention must have any one of the following requirements: ・ Higher aliphatic amine ethylene oxide adduct is oleylamine, cocoalkylamine, soybean alkylamine, beef tallow alkylamine, and cured tallow alkylamine. An ethylene oxide adduct of higher aliphatic amines selected from: and mixtures thereof; and the higher fatty acid amide ethylene oxide adduct is selected from oleylamide, cocoalkylamide, soy alkylamide, beef tallow alkylamide and hardened tallow alkylamide The above-mentioned effects are further exhibited when the ethylene oxide adduct of higher fatty acid amide and the mixture thereof are satisfied.

It is the schematic which shows the basic flow of the water treatment facility of a coke plant. It is a figure which shows transition of the amount of SS in the water and the amount of oil before and after the addition of the antifouling agent of Example 1 of Test Example 3.

The antifouling agent (hereinafter also referred to as “antifouling agent”) for the water-safety treatment facility of the present invention comprises at least one selected from higher aliphatic amine ethylene oxide adducts and higher fatty acid amide ethylene oxide adducts as antifouling components. It is characterized by containing.
“Anhydrous” is also referred to as “gas liquid” and means water which is condensed and separated from coal gas and dissolved in free ammonia, ammonium salt and a small amount of phenols.

  Examples of the safety treatment facility include facilities used for the treatment of high-temperature gas (COG) generated from a coke oven such as an ironworks.

  The higher aliphatic amine ethylene oxide adduct and higher fatty acid amide ethylene oxide adduct, which are the antifouling components of the antifouling agent of the present invention, have both nonionic (nonionic) surfactant and cationic surfactant properties. It is considered that the properties contribute to the effects of the present invention.

A higher aliphatic amine ethylene oxide adduct (polyoxyethylene alkylamine) can be obtained by reacting a higher aliphatic amine and ethylene oxide in the presence or absence of an alkali catalyst such as sodium hydroxide.
In the present invention, the “higher” of the higher fatty acid amine means about 12 to 24 carbon atoms.
In the above reaction, 2 mol of ethylene oxide is added to the nitrogen atom of 1 mol of a higher aliphatic primary amine, and an ethylene glycol chain grows to obtain a higher aliphatic tertiary amine.
This tertiary amine has both nonionic and cationic properties and is considered to exhibit the effects of the present invention as described above.

  Such higher aliphatic amine ethylene oxide adducts include, for example, higher aliphatic selected from dodecylamine, palmitylamine, stearylamine, oleylamine, cocoalkylamine, soy alkylamine, beef tallow alkylamine and hardened tallow alkylamine. Mention may be made of ethylene oxide adducts of amines.

The above coco alkyl amine, soybean alkyl amine, beef tallow alkyl amine and hydrogenated beef tallow alkyl amine are amines made from coconut oil, soybean oil, beef tallow and hard beef tallow, respectively, and are a mixture of aliphatic amines having different carbon numbers. .
Here, “alkylamine” means a monoalkyl primary amine, but a secondary amine or a tertiary amine may be contained as long as the effects of the present invention are not impaired.
Higher aliphatic amines of higher aliphatic amine ethylene oxide adducts include saturated aliphatic amines such as alkylamines and unsaturated aliphatic amines such as alkenylamines, but have partially unsaturated bonds. Ethylene oxide adducts of aliphatic amines are also marketed as alkylamine ethylene oxide adducts. For example, polyoxyethylene oleylamine is marketed as polyoxyethylene alkylamine.

In the present invention, commercial products of the above higher aliphatic amine ethylene oxide adducts can be used, and one of these can be used alone or in combination of two or more.
Among the above higher aliphatic amine ethylene oxide adducts, a higher aliphatic selected from oleylamine, cocoalkylamine, soybean alkylamine, beef tallow alkylamine, and hardened tallow alkylamine in terms of the effects of the present invention and availability. Particularly preferred are amine oxide adducts of amines as well as mixtures thereof.

A higher fatty acid amide ethylene oxide adduct (polyoxyethylene fatty acid amide) can be obtained by reacting a higher fatty acid amide and ethylene oxide in the presence of an alkali catalyst such as sodium hydroxide.
In the present invention, the “higher” of the higher fatty acid amide means about 12 to 24 carbon atoms.
In the above reaction, 2 mol of ethylene oxide is added to the nitrogen atom of 1 mol of a higher aliphatic primary amide, and an ethylene glycol chain grows to obtain a higher aliphatic tertiary amide.
This tertiary amide has both nonionic and cationic properties and is considered to exhibit the effects of the present invention as described above.

  Examples of such higher fatty acid amide ethylene oxide adducts include caprylic acid amide, lauric acid amide, palmitic acid amide, stearic acid amide, oleic acid amide, coco alkyl amide, soybean alkyl amide, beef tallow alkyl amide, and cured beef tallow alkyl amide. And ethylene oxide adducts of fatty acid amides selected from:

The above coco alkyl amide, soybean alkyl amide, beef tallow alkyl amide and hydrogenated beef tallow alkyl amide are fatty acid amides made from coconut oil, soybean oil, beef tallow and hard beef tallow, respectively, and are mixtures of aliphatic amines having different carbon numbers. is there.
Here, “alkylamide” means a primary amide, but a secondary amide or a tertiary amine may be contained as long as the effects of the present invention are not impaired.

In the present invention, commercially available products of the above higher fatty acid amide ethylene oxide adducts can be used, and one of these can be used alone or in combination of two or more.
Among the above higher fatty acid amide ethylene oxide adducts, higher fatty acid amides selected from oleyl amide, coco alkyl amide, soybean alkyl amide, beef tallow alkyl amide, and hardened tallow alkyl amide in terms of the effect of the present invention and availability. Especially preferred are the ethylene oxide adducts and mixtures thereof.

  The antifouling agent of the present invention comprises the above antifouling component and an aqueous solution thereof, and may contain a known surfactant, antifoaming agent, organic solvent and the like as long as the effects of the present invention are not impaired.

Examples of the surfactant include a polyethylene glycol type nonionic surfactant, a polyhydric alcohol type nonionic surfactant, a carboxylate type anionic surfactant, a sulfonate type anionic surfactant, and a sulfate ester type interface. Examples thereof include surfactants, phosphate ester type surfactants, amino acid type amphoteric surfactants, betaine type amphoteric surfactants, and quaternary ammonium salt type cationic surfactants.
Examples of the antifoaming agent include a lower alcohol defoaming agent, a silicone defoaming agent, a mineral oil defoaming agent, a higher alcohol surfactant, and a higher fatty acid surfactant.
Examples of the organic solvent include alkylbenzene, light oil distilled from crude oil and naphtha, and the like.

  The antifouling method for the water-safe treatment facility of the present invention (hereinafter also referred to as “fouling prevention method”) comprises the anti-fouling agent of the present invention, wherein the anti-stain component is 10 to 500 g relative to tar in the water of the water-proof treatment facility. It is characterized in that the tar emulsion in the aqueous water is separated into a tar phase and an aqueous phase and the contamination of the aquatic treatment facility is prevented.

If the antifouling component is less than 10 g / ton relative to tar in the water of the water treatment facility, the effects of the present invention may not be sufficiently obtained. On the other hand, when the antifouling component exceeds 500 g / ton with respect to tar in the water of the water treatment facility, the effect of the emulsion breaker (demulsification) of the present invention cannot be obtained, and on the contrary, emulsification is promoted. is there.
A preferable addition ratio of the antifouling component is 50 to 200 g / ton with respect to tar in the aqueduct water of an aquatic treatment facility.

  The dirt prevention method of the present invention achieves these because it is an object to obtain the effect of separating the tar emulsion in the aqueous water into the tar phase and the aqueous phase and the effect of preventing the aqueous treatment equipment from being soiled. If possible, the antifouling agent of the present invention may be added anywhere as long as it is a circulation path for the water-safe treatment facility.

FIG. 1 is a schematic diagram showing a basic flow of a water treatment facility for a coke plant.
In the figure, each figure number 1 is a coke oven, 2 is a dry main, 3 is a coke decanter, 4 is circulating water, 5 is indirect water, 6 is direct cooling, 7 is a super decanter, and 8 is a tar tank. .
As a place where the antifouling agent of the present invention is added, a line for circulating the aqueous water in order to remove and wash the deposits without stopping the operation of the aquatic treatment facility and reduce the blockage of the spray nozzle of the dry main body, It is particularly desirable to add it to the dry water return line of the dry main. For example, in FIG. 1, A point and B point are mentioned, A point is preferable. The temperature of the aqueous solution to which the antifouling agent of the present invention is added is about 25 to 50 ° C. at point A.

  The present invention will be specifically described with formulation examples, comparative formulation examples, and test examples, but the present invention is not limited thereto.

(Formulation example 1)
Ethylene oxide adduct of oleylamine (cationic, manufactured by Nalco, product name: Nalco 71700)
(Comparative formulation example 1)
Dioleyldimethylammonium chloride (cationic, manufactured by Lion Akzo Co., Ltd., product name: ARCARD 2O-75)
(Comparative formulation example 2)
Sodium dodecylbenzenesulfonate (anionic, manufactured by Nalco, product name: Nalco 7719)
(Comparative formulation example 3)
Nonylphenol ethylene oxide adduct (non-ionic, manufactured by Nippon Emulsifier Co., Ltd., product name: New Coal 564)
(Comparative formulation example 4)
Polyoxyethylene polyoxypropylene block copolymer (non-ionic, manufactured by Sanyo Chemical Co., Ltd., product name: New Pole PE-64)

(Test Example 1: Emulsion braking confirmation test)
The effect of emulsion breaking when Formulation Example 1 and Comparative Formulation Examples 1 to 4 were added to the emulsion at the ratio (addition concentration) shown in Table 1 was evaluated.
In the test, tar and circulating low water collected separately from the actual equipment of the water treatment facility of the coke plant at a steel company were used.
First, the tar and the aqueous solution are put into a stirring mixer having a capacity of about 1 L at a weight ratio of 3: 7, and stirred for 10 minutes at a rotational speed of 5,500 rpm using a homomixer. ) Was prepared.

The obtained emulsion was put into a graduated 100 mL test tube, each formulation was added at the ratio shown in Table 1, and the test tube was shaken up and down for 1 minute by hand. After stirring, leave still for 30 minutes, position of the interface between the water layer and the oil layer containing the emulsion after 10 minutes, 20 minutes and 30 minutes (volume of test tube: ml) and 30 minutes after the start of standing The state of the supernatant was observed.
The test was conducted in a state where the tar, the water and the emulsion were kept warm so as not to be 60 ° C. or lower.
Moreover, the blank test was done on the same conditions about no formulation addition.
The obtained results are shown in Table 1 for both the additive preparation and the additive concentration.

  From the results of Table 1, although there is an improvement in oil / water separation under any condition as compared to the system without the addition of a drug (blank of Comparative Example 1-5), the tar and the most under the conditions of Examples 1-1 to 1-3 It can be seen that the water is separated and the supernatant is well-cleaned.

(Test Example 2: Dry main nozzle clogging frequency reduction effect confirmation test)
The frequency of clogging of the dry main nozzle when adding formulation example 1 and comparative formulation examples 1 to 4 in the ratio (addition concentration) shown in Table 2 in the water treatment facilities 1 to 6 of a coke plant of a steel company The reduction effect was evaluated.
The obtained results are shown in Table 2 for the additive preparation and the additive concentration.

  From the results of Table 2, in Examples 2-1 to 2-11 in which Formulation Example 1 was added at one or two concentrations, Comparative Examples 2-1 to 2-7 in which Comparative Formulation Examples 1 to 4 were added were used. It can also be seen that the nozzle clogging frequency is improved and the number of cleanings can be reduced.

(Test Example 3: Aqueous water cleaning effect confirmation test)
Formulation Example 1 was added at a rate of 165 mg / L (150 g / ton) to tar in the aqueduct to the upstream side of the coke decanter of the coke decanter of the coke plant at a steel company. Then, the cleaning effect of the safe water was evaluated.
In addition, the chemical | medical agent corresponding to the comparative formulation example 1 was added to the water treatment facility of the coke plant before adding the formulation example 1.
Measure the amount of suspended solids (SS amount) and hexane extract amount (oil amount) before and after the formulation addition over time according to JIS K0102 “Factory drainage test method” to evaluate the oil separation effect. (Example 1).
The obtained results are shown in FIG.

  From the results of FIG. 2, it can be seen that immediately after the addition of Formulation Example 1, the amount of SS and the amount of oil temporarily increased, and thereafter decreased and remained low. This is because tar accumulated in the system of the water treatment facility peels off due to the addition of Formulation Example 1 and temporarily increases the amount of SS and the amount of oil, and then decreases due to the addition effect of Formulation Example 1. It is thought that.

1 Coke Oven 2 Dry Main 3 Coke Decanter 4 Circulating Aqueous Water 5 Indirect Aqueous Water 6 Direct Cooling 7 Super Decanter 8 Tar Tank A, B Chemical Addition Position

Claims (4)

  An antifouling agent for water-resistant treatment facilities, comprising at least one selected from a higher aliphatic amine ethylene oxide adduct and a higher fatty acid amide ethylene oxide adduct as an antifouling component.   The higher aliphatic amine ethylene oxide adduct is an ethylene oxide adduct of a higher aliphatic amine selected from oleylamine, cocoalkylamine, soybean alkylamine, beef tallow alkylamine and hardened tallow alkylamine and mixtures thereof. Antifouling agent for the water-safe treatment facility described.   3. The higher fatty acid amide ethylene oxide adduct is an ethylene oxide adduct of a higher fatty acid amide selected from oleylamide, cocoalkylamide, soybean alkylamide, beef tallow alkylamide, and hardened tallow alkylamide, and mixtures thereof. Antifouling agent for water-safe treatment facilities as described in 1.   The antifouling agent according to any one of claims 1 to 3 is added so that the antifouling component is in a ratio of 10 to 500 g / ton with respect to tar in the low water of the low water treatment facility, A method for preventing fouling of a water treatment facility, comprising separating a tar emulsion in the aquatic water into a tar phase and a water phase, and preventing fouling of the water treatment facility.