JPS61129034A - Outflow oil treatment agent - Google Patents

Abstract

PURPOSE:To markedly reduce fish toxicity, by preparating an outflow oil treat ment agent on the basis of a surfactant obtained by further esterifying at least a part of the hydroxy group of the alkylene oxide adduct of sorbitan alkyl ester. CONSTITUTION:60wt% of a surfactant obtained by further esterifying at least a part of the hydroxyl group of the alkylene oxide adduct of sorbitan alkel ester is contained and a non-pertroleum type solvent is compounded as a solvent to prepare an outflow oil treatment agent. As sorbitan alkyl eser, eser of sorbitan and 12-18C fatty acid is pref. and, as alkylene oxide, ethylene oxide is pref. and the addition mol number thereof is pref. 20-40. As the non- petroleum type solvent, a high ignition point ester solvent is pref. and, for example, there is monoester of monovalent carboxylic acid and monohydric alcohol or monoester of monovalent carboxylic acid and polyhydric alcohol.

Description

[Detailed description of the invention] Breasts! FIELD OF THE INVENTION The present invention relates to an oil spill treatment agent, particularly a low fish toxicity oil spill treatment agent. Furthermore, the present invention relates to a surfactant with low fish toxicity suitable for obtaining an oil spill treatment agent containing a high concentration of surfactant components.

Problems to be solved by the prior art and the invention As a method for treating oil spilled onto the sea surface due to tanker accidents, etc., a pond floating at the interface is transported to a recovery ship 1- by a pump or the like.
! l! Methods that have been used for a long time include the method of collecting the oil, the method of adsorbing and treating it with adsorbents such as Munoro and Motsupu, and the method of spraying spilled oil dispersants to emulsify the area in seawater and allowing it to settle. .

The method of using spill M1 treatment agent is the most popular method as it is easy to work with, but due to the amount of surfactant contained in the spill oil treatment agent, it can cause damage to fish, shellfish, and algae. The problem that needs to be solved is to give For this reason, research into oil spill treatment agents with low toxicity to fish and surfactants, which are raw materials thereof, has been actively conducted11. Surfactant 11, which is generally known as having low toxicity to fish, is used as a raw material for oil spill treatment.
Polyglycerino alkyl esters, polyethylene glycol alkyl esters, etc., have an indicator of fish toxicity, 'rLm24 (ali', which causes half of the fish to die in 24 hours), which is around 3000p1111 at most, and lower fish There are no known oil spill treatment agents that use toxic surfactants as raw materials. Sucrose esters and the like have even more paper fish nI properties than these, but cannot be used because they have poor emulsifying properties for spilled oil.

On the other hand, the spilled At + treatment agent is transported by ship to the spill site in case of an unexpected accident, so it is always stored in a warehouse near the port, so it is kept in a state with the highest possible treatment capacity, that is, diluted with seawater, etc. If possible, there is a tendency for a surfactant (a surfactant that contributes to emulsification) with a high 0 degree content to be desired. Conventionally, spilled oil dispersants have used inexpensive surfactants and petroleum oils such as kerosene, which have excellent compatibility with spilled oils (crude oil, heavy oil, etc.). Kerosene, especially n-paraffin, which is widely used because it has low toxicity and is easily decomposed by microorganisms, has a low solubility of surfactant, so the amount of surfactant used is usually about 20%.

Therefore, five times the storage volume of the surfactant theoretically required for oil spill treatment is required, and five times the amount of cargo is required.

It would be possible to create an oil spill treatment agent with a higher concentration of surfactant by selecting an appropriate solvent, but at present, it is impossible to prevent seashore dyeing. According to the Ura Treatment Agent Performance Test Standards, the fish + 1 # property of spilled oil treatment agents is regulated by the i' L m of the spilled oil treatment agent itself, so the surfactant concentration in the treatment agent There was a limit to how much the TLm could be raised (up y?4-).

Due to the essential properties required of a spilled oil dispersant and the reasons mentioned above, it has lower toxicity to fish and is less toxic than the spilled Ab.
The development of a surfactant that is immersed in L-forming properties was an urgent issue in terms of light policy.

Means for Solving the Problems The present invention provides that even if a single surfactant in which at least a portion of the hydroxyl groups of the oxidized alkylene adduct of a sorbitan alkyl ester is further esterified, the surfactant can be used as a single product.
It was found that fish with extremely low Lm24 of about 6,000 ppm or more have a very low J1 property, and that this affects the emulsification treatment of spilled oil.

The present invention mainly consists of a surfactant (hereinafter referred to as the active agent of the present invention) in which at least one of the alkylene oxide adducts of a sorbitan alkyl ester is further converted into a hydroxyl. Concerning the effluent M1 treatment waste containing as a component <-i 4'.

The active agent of the present invention itself is a new surfactant, and its properties are completely unknown.

The sorbitan alkyl ester of the present invention is obtained by esterifying sorbitan with a suitable fatty acid.
1 to 3, preferably 1 hydroxyl group with 8 to 2 carbon atoms
2, preferably esterified with 12 to 18 fatty acids (saturated or unsaturated). Sorbitan is 1.5-
It may be sorbitan, 3.6-sorbitan, 1.4-sorbitan or mixtures thereof. It is typically known by the trade name Span.

Sorbitan alkyl esters are reacted with alkylene oxides to form alkylene oxide adducts of sorbitan alkyl esters of the type known under the trade name TOWIN. The alkylene oxide is mainly ethylene oxide, but a portion of propylene oxide may also be used if the alkylene oxide is secondary. The f-T mole number of ethylene oxide, the amount of fatty acid used in the first esterification or subsequent esterification, the molecular weight of the fatty acid, and the desired 1-IL[3(I11 aqueous and lipophilicity) of the activator of the present invention. The ffQ can be selected depending on the balance of
0 mol is preferred.

At least a portion of the hydroxyl groups of the alkylene oxide adduct of the turbitan alkyl ester are further esterified with a suitable fatty acid. This esterification significantly reduces fish toxicity.

Esterification is not particularly limited, but has 4 to 22 carbon atoms,
More preferably 8-20, especially 12-18 fatty acids are used. Particularly preferred fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid,
These include elaidic acid, linoleic acid, erucic acid, and linoleic acid. Esterification should be carried out to block all hydroxyl groups, but from the viewpoint of emulsifying properties of spilled oil, on average 1 hydroxyl group per molecule should be carried out.
It is preferable to make 4-ru so that ~2 bets remain. In the case of alkylene oxide adducts with 1411 hydroxyl JI (:N/BT), esterification is carried out once, and in the case of alkylene oxide adducts with 3 hydroxyl chains (T, it is preferable to carry out esterification of 1 to 2 esters).

The type and amount of fatty acid used for esterification may be appropriately selected depending on the emulsifying property of the spilled oil.

Typical addition molar failure of llb acid and ethylene oxide and HL
The relationship with r3 is listed in Table 1. HLB suitable for emulsifying spilled oil from batteries, crude oil, etc. is generally about 9 to 12.

Furthermore, two or more active agents of the present invention having different IL3 may be blended to obtain the above-mentioned HLB, and in addition to the active agent of the present invention, a conventional low fish toxicity surfactant may be blended.

A second advantage of using the activator of the present invention is that a highly concentrated oil spill treatment agent can be obtained. As mentioned above, the concentration of conventional spilled oil dispersants is about 20%, and raising the f5 degree beyond this level would increase the fish toxicity of the spilled oil dispersants, which was not appropriate.

The activity of the present invention is 11 lower than that of conventional activators for oil spill treatment.
; can be made to high concentrations. Since the spilled oil dispersant is diluted with water or directly spilled oil when used, its viscosity is preferably 70 to 50 cps or less at 7AL. Therefore, it is preferable that the activator of the present invention is also diluted with a suitable diluent to lower its viscosity.

However, when conventionally used kerosene is diluted, for example, by 4 degrees to give an activator f5 degree of about 60%, the activator; At portion and the solvent portion tend to separate over time. For this reason, the viscosity of the effluent fib treatment agent decreases with a small amount, resulting in less fish 111 properties. A solvent that has high affinity with the emulsifying agent and does not impair emulsifying properties is required.

In addition, in accordance with IfIN/TlIj Dyeing and Prevention City Law Enforcement 11 Current Regulations, Spilled Oil Disposal ~ 1 is regulated by the Fire Service Law Hazardous Materials Handling Standards, Category 4, Class 3 A, All flashpoints of 7J+ or higher. Ester-based solvents are preferable as such solvents, and mono- or diester-based solvents having a total carbon number of approximately II or more, particularly 17 or more and up to 36 are preferable. If the number of carbon atoms is less than 9, the flash point will be 61° C. or lower, and the dispersant performance test standard will not be passed. If the carbon number is 17 or more, the flash point will be the same as the Fire Service Act Hazardous Materials Handling Standards [No. 4].
It falls under petroleum, and the storage capacity will increase as the warehouse storage m will be up to 3000.9 liters (up to 2000 liters for third class petroleum such as kerosene). Therefore, it becomes easier to deal with sudden oil spill accidents. Moreover, if the carbon number exceeds 40, the viscosity will increase and this is not suitable.

Examples of ester solvents include monoesters such as monoesters of -carboxylic acids and -&+1i alcohols or monoesters of monocarboxylic acids and polyhydric alcohols, and diesters such as polycarboxylic acids and monohydric alcohols. Examples include tonori esters and diesters of polyhydric carboxylic acids and polyhydric alcohols.

Among the above esters, isopropyl myristate, nooctyl maleate, isopropyl oleate, methyl oleate, methyl laurate, methyl oleate, dioctyl phthalate, nooctyl fumarate, noethyl phthalate, dimedyl fumarate, etc. preferable. These esters have a high flash point, are highly compatible with the activator of the present invention, and can reduce the viscosity well even when used in small amounts, making it possible to obtain an oil spill treatment agent containing a high concentration of the activator of the present invention. In addition, spilled oil treatment performance is not reduced.

Hereinafter, the present invention will be explained with reference to Examples.

Kame 4 Shin (Production of activator of the present invention) 8 g of I"I' 32 was added to 327 g of polyoxyethylene (20 mol) sorbitan monooleate ('l"wecn 80) l and 565 g of oleic acid, and the mixture was heated under a nitrogen atmosphere. Heat to 190°C and react for 5 hours. il
The acid value of the reaction product was 1 G, and the color was yellowish brown 1III.
(25°C), and III, r3 was 11.0.

Polyoxyethylene (20 mol) Monooleate Polyoxyethylene (20 mol) Sorbitan Monooleate (
PTS was added to 1327 g of Tweei 80) and 283 g of oleic acid, and the mixture was stirred and reacted at 190° C. for 3 hours under a nitrogen atmosphere. The acid value of the reaction product obtained was 1.5, and H
A tan reaction product with LB of 13.0 was obtained.

Example 11 and 4; -q-η A spilled oil dispersant was prepared using the active agents [+] and [11] of the present invention according to the following formulation (formulation value: Nail!!1).

1. Recording power spilled oil treatment ~ Viscosity, flash point, fish using 1.
11 properties and emulsification rate were evaluated.

(1) Viscosity: JIS K2283 (2) Flash point, 115K2265 Pensky Martens (3) Fish toxicity: JIS K-0102-55 (4) Emulsification rate (%)/Marine dye resistance I1. ．． Law Enforcement Regulations (Showa 4
Dispersant performance test (Ministry of Transport Ordinance No. 38, 2006) Oil dispersant performance test
Accurately add 50 zlj of target water and 2 x q of dispersant mixed oil to 1 W, and shake vertically for 5 minutes with a shaker for 3 oz.
After shaking at an amplitude of 401 IN, one piece was left standing for 30 seconds, and the other piece was left standing for 10 minutes. After standing still, remove the emulsified layer from the bottom of the separatory funnel for about 30 minutes.
Take it out and collect it in a beaker.

While stirring the collected emulsified layer, accurately collect 25 zlj into a new branched funnel using a pipette.

To this, add about 37% of carnow chloride 11, and add 11% carbon tetrachloride (
Extract the oil in the emulsified layer with 1+0 and repeat the 1lll:li operation two more times. Combine the extracted carbon tetrachloride layers, add an appropriate amount of anhydrous sodium sulfate to dehydrate, and add isopyl alcohol 5z to make it transparent.
A layer of carbon tetrachloride is added to the surface to give an overall view of 50x (l).

The absorbance of this was measured at a wavelength of G50n, s, and the extract 2
Oil content in 5ml+F! i CRQ) and calculate the emulsification rate using the following formula: 2 x 10/12 x 60 after 2515230 seconds
% or more, and 20% or more after 10 minutes is considered to be a pass.

The results obtained are shown in Table-2.

/J-2 *1 ・ Uses incoming A11 (light oil) *2 ・ Uses C previous song (heavy oil) *3: N5C92,5% Mg (4,・GIIIO+, 1% NatSOt O, 4%C5GJ
, m ・6Ht0 0. I 6% water
Zan-bro! l11g effect By using the activator of the present invention, it is possible to obtain a spilled oil dispersant with significantly low fish toxicity, and as a result, it can be made into a highly concentrated oil spilled dispersant, so it can be stored in warehouses and sent to spilled oil treatment ships. The product (RmC vs. per surfactant) can be significantly increased by 4°. In addition, a low-viscosity oil dispersant can be obtained even in a vertical position, and can be sprayed directly at the spill site.
It becomes possible to spray on-site from an airplane, etc.

Claims (1)

[Scope of Claims] 1. A spilled oil treatment agent containing as a main component a surfactant obtained by further esterifying at least a portion of the hydroxyl groups of an alkylene oxide adduct of a sorbitan alkyl ester. 2. The spilled oil treatment agent according to item 1, wherein the sorbitan alkyl ester is a sorbitan monoalkyl ester. 3. The spilled oil treatment agent according to item 1, wherein the alkylene oxide is ethylene oxide. 4. Third, the number of added moles of ethylene oxide is 20 to 40
Oil spill treatment agent as described in section. 5. The spilled oil treatment agent according to item 1, wherein the sorbitan alkyl ester is an ester of sorbitan and a fatty acid having 12 to 18 carbon atoms. 6. The spilled oil treatment agent according to item 1, wherein one or two of the hydroxyl groups of the ethylene oxide adduct are esterified. 7. Ester of ethylene oxide adduct has 12 to 18 carbon atoms
2. The oil spill treatment agent according to claim 1, which is an ester of a fatty acid. 8. The spilled oil treatment agent according to item 1, which contains at least 60% by weight of a surfactant obtained by further esterifying at least a portion of the hydroxyl groups of the alkylene oxide adduct of sorbitan alkyl ester, and uses a non-petroleum solvent as a solvent. . 9. First, the non-petroleum solvent is a high flash point ester solvent
Oil spill treatment agent as described in section.