JPS60212480A - Agent for treating spilled oil - Google Patents

Abstract

PURPOSE:To provide an agent for treating spilled oil on the surface of the sea, having high emulsifying and dispersing power and safety, etc., by compounding a polyoxyalkylene polyhydric alocohol polyresin acid ester, sodium dioctylsulfosuccinate, a water-soluble solvent and water at specific ratios. CONSTITUTION:The objecive treating agent can be prepared by compounding (A) a surfactant obtained by compounding (i) a polyoxylakylene polyhydric alcohol polyfatty acid ester of formula [R is 11-21C alkyl or alkenyl; l is 1,5-(m-1); A is polyhydric alcohol residue; R' is -CH2CH2O- or -CH(CH3)CH2O-; m is number of OH groups of the polyhydric alcohol; n is molar number of added R'] and (ii) sodium dioctylsulfosuccinate at a weight ratio of (1.5-15):1 [preferably (2-10):1], with (B) a water-soluble solvent (e.g. diethylene glycol monoethyl ether, etc.) and (C) water. The weight ratios of A:B:C is (2-60):(0-50):(10-98), and that of A:B is preferably (5-40):(3-30).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is a spilled oil dispersant that emulsifies and disperses oil spilled on the sea to dissipate it from the sea surface. The present invention relates to a water-soluble oil spill treatment agent.

Accidents in which oils such as crude oil and heavy oil spill onto the sea surface have become a major social problem as they cause environmental damage and other pollution. For this reason, oils spilled onto the sea are recovered using oil adsorbents or gelling agents, or emulsified and dispersed into seawater using spilled oil dispersants. Normally, it is best to recover spilled oil, but in the open ocean or when the sea is rough, it is almost impossible to recover the oil. Many treatment methods are used to emulsify and disperse oil spilled into seawater. Currently, a large number of oil spill treatment agents are commercially available in Japan, and these conventional oil spill treatment agents are generally composed of a surfactant and a hydrocarbon solvent such as paraffinic mineral oil. In this way, the hydrocarbon solvent blended into the spilled oil dispersant as a diluting solvent for the surfactant has the effect of adjusting the viscosity of the spilled oil dispersant and promoting the emulsifying and dispersing power of the surfactant. Even if it is accepted, the content of hydrocarbon solvents in oil spill treatment agents is usually around 60-9.
Because of its extremely high content of 5% by weight, conventional oil spill treatment agents have various problems. The first problem is that most of the hydrocarbon solvents used in spilled oil dispersants are flammable, dangerous substances that are classified as Class 4 hazardous materials under the Fire Service Act. Conventional spilled oil dispersants are highly dangerous to humans, and the storage pipes for spilled oil dispersants are subject to restrictions under the Fire Service Act. The second problem is that although hydrocarbon solvents do not have the essential function of emulsifying and dispersing oil like surfactants, they are contained in large amounts in spilled oil dispersants. This is uneconomical and causes manufacturing costs to rise more than necessary. The third problem is that since spilled oil dispersants are used by spraying on spilled oil floating on the sea, the use of conventional spilled oil dispersants that contain a large amount of hydrocarbon solvents, which are the main component of emulsification, is This also means that unnecessary organic matter is being dumped into the sea, which in turn causes a large burden on the biodegradation of the oil that has been emulsified and dispersed into the sea, creating a large burden on the ocean, resulting in marine pollution. This is not at all desirable from the standpoint of prevention.

The present invention aims to solve the above-mentioned problems and provide a spilled oil dispersant that has excellent emulsifying and dispersing performance for spilled oil.The spilled oil dispersant of the present invention uses water as a diluent. It is possible to disperse spilled oil into seawater with a small amount of additive, has low toxicity, has little risk of ignition, and is easily soluble in water in any proportion, and is similar to conventional spilled oil. It has characteristics such as being more economically advantageous than processing agents.

In particular, as will be clearly shown in the examples below, it can be used as a spilled oil treatment agent for water-soluble threads, and in addition, charcoal 4e, tjc 8. ,
The present invention makes it possible for the first time to develop a spilled oil dispersant that has emulsifying and dispersing performance equivalent to or better than conventional spilled oil dispersants containing @ agents and can be less toxic.

The present invention relates to a polyhydric alcohol polyfatty acid ester (RCOO friend A -) OH) represented by the following general formula. -21;
[In the formula, A represents a polyhydric alcohol residue, R is an alkyl group or alkenyl group having 11 to 21 carbon atoms, t is the number of ester groups from 1.5 to (to-1), and m represents the number of hydroxyl groups in the polyhydric alcohol, and is an integer of at least 3. ] An interface consisting of blending polyoxyalkylene polyhydric alcohol polyfatty acid ester obtained by adding ethylene oxide and propylene oxide with sodium dioctyl sulfosuccinate in a weight ratio of 1.5:1 to 15=1. Activator 2-60% by weight, water-soluble solvent 0-
It is a water-soluble oil spill treatment agent that is composed of 50% by weight and water, and is characterized in that the water content is 10-98% by weight.

The polyhydric alcohol polyfatty acid ester represented by the above general formula can be easily obtained by commonly causing a condensation reaction between a polyhydric alcohol and a fatty acid using a known synthesis method. The polyhydric alcohol in this case is a polyhydric alcohol having at least 3 hydroxyl groups in the molecule, preferably a polyhydric alcohol having 3 to 6 hydroxyl groups in the molecule, such as glycerin, diglycerin, trimethylolpropane, sorbitol. , sorbitan, mannitol, pentaerythritol and the like are suitable. Fatty acids are saturated or unsaturated fatty acids with 12-22 carbon atoms,
Oleic acid is most preferred in terms of emulsifying properties and emulsion stability. Regarding ester superimposition, it is preferable to use sesquiester or higher, preferably diester or higher, from the viewpoint of emulsification performance. However, since ethylene oxide and propylene oxide are further added to this polyhydric alcohol polyfatty acid ester in a later step, it is necessary to leave at least one hydroxyl group in the molecule.

The polyoxyalkylene polyhydric alcohol polyfatty acid ester can be easily synthesized by subjecting the polyhydric alcohol polyfatty acid ester to an addition reaction of ethylene oxide and propylene oxide in a conventional manner under pressurized conditions.

In this case, the addition method of ethylene oxide and propylene oxide may be either block addition or random addition, but preferably random addition. The addition ratio of ethylene oxide and propylene oxide is preferably 50-90i% by weight of ethylene oxide and 50-10% by weight of propylene oxide, so that the total number of moles of ethylene oxide added and the number of moles added of propylene oxide is 15-50 moles. This is the range.

Thus, the polyoxyalkylene polyhydric alcohol polyfatty acid ester obtained by adding ethylene oxide and propylene oxide to the polyhydric alcohol polyfatty acid ester can be used especially in combination with sodium dioctyl sulfosuccinate to remove spilled oil, especially B heavy oil. It has excellent characteristics as an emulsifying and dispersing agent, such as exhibiting excellent emulsifying and dispersing properties for heavy oils such as and C heavy oil, and also exhibiting good emulsifying and dispersing properties even under weak stirring conditions.

As the sodium dioctyl sulfosuccinate to be blended with the polyoxyalkylene polyhydric alcohol polyfatty acid ester, commercially available products such as Nyalol CT-1 manufactured by Toho Chemical Industry Co., Ltd. can be used.

The mixing ratio of polyoxyalkylene polyhydric alcohol polyfatty acid ester and sodium dioctyl sulfosuccinate in the surfactant is in the range of 1.5:1 to 15:1 by weight, preferably 2:1 to 10:1. It is. If the blending ratio of sodium dioctyl sulfosuccinate is lower than the above blending ratio range, light oils can be easily emulsified and dispersed, but heavy oils have good emulsifying and dispersing ability under weak stirring. I can't get it. On the other hand, if the amount is increased, not only will the emulsifying dispersibility not be improved, but the fish toxicity will also become stronger, which is not preferable.

Polyoxyalkylene polyhydric alcohol polyfatty acid ester and sodium dioctyl sulfosuccine do not provide sufficient emulsifying performance, and if the upper limit of the range is exceeded, the viscosity of the spilled oil dispersant will increase and workability will deteriorate, which is undesirable. .

Furthermore, since the oil spill treatment agent of the present invention is arbitrarily soluble in water,
By increasing the surfactant content to 30% by weight or more,
It may also be a concentrated oil spill treatment agent that is diluted with water to an appropriate concentration before use at the oil spill treatment site.

Examples of water-soluble solvents include ethyl alcohol, inpropyl alcohol, normal propyl alcohol, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether.

These water bathing solvents have the effect of lowering the viscosity when the water content in the spilled oil dispersant of the present invention is low, and when the water content is high, the spilled oil dispersant of the present invention may spoil. It also works to prevent this from happening. The content of water-soluble solvent is 0-7
50% by weight, preferably 3-30% by weight.

The water content in the spilled oil dispersant of the present invention is lo-98% by weight. As the water content increases, the flash point of the spilled oil dispersant increases, and although it varies depending on the type of water-soluble solvent used and the amount used, the water content is approximately 15% by weight.
If the temperature exceeds 1, there is almost no risk of ignition.
5 weight t% or more is desirable.

Examples of synthesis of nonionic surfactants and specific examples of spilled oil dispersants are shown below. It can be understood from this example that the oil spill treatment agent according to the present invention exhibits excellent oil emulsification and emulsion stability even when added in small amounts.

0 Synthesis of nonionic surfactant Synthesis Example 1 Sorbitan trioleate 967.9 (1.0 mol) and potassium hydroxide 3.6 g (0,064 mol) were charged into a 5 t autoclave and heated, and the mixture was heated to 110 mol under reduced pressure.
Dehydration was performed at 120°C for 30 minutes. After that, ethylene oxide 994.49 (22.6 mol) and propylene oxide 429.2j' (7.4 mol) were uniformly mixed in advance, and then heated at 140-150°C and 3 Kg/cr.
The introduction took 4 hours under a pressure of less than /l. After the introduction was completed, the pressure was increased to 5 Kf/- with nitrogen, and the reaction mixture was aged at 150° C. for 1 hour to obtain a reaction adduct of 02382fI, which was considered to have completed the reaction.

Synthesis Example 2 Sorbitan trioleate 967j' (1.0 mol),
By the method described in Synthesis Example 1 using potassium hydroxide 3.919 (0.07 mol), ethylene oxide 1328.8.9 (30.2 mol) and propylene oxide 568.4j' (9.8 mol). Synthesize and react adduct 2
848.9 was obtained.

Synthesis Example 3 Using glycerin dioleate 62019 (1.0 mol), potassium hydroxide 1.719 (0.03 mol), ethylene oxide 704 g (16.0 mol) and propylene oxide 232AI (4.0 mol) Synthesis example 1
The reaction adduct 1543F was synthesized by the method described in .

Next, an example using the surfactant obtained in the synthesis example will be shown. As sodium dioctyl sulfosuccinate, Eyarol CT-1, a product of Toho Chemical Industry (■), was used. The composition of this air roll CT-1 is as follows.

Eyarol CT-1 Sodium dioctyl sulfosuccinate 70% Propylene glycol 15% Water 15% Example 1 Nonionic surfactant of Synthesis Example 1 25 yarol CT
-15T.

Diethylene glycol) Monomethyl Nigale 25% Water 45% Example 2 Nonionic surfactant of Synthesis Example 1 4.0 Cheyarol C
T-11.5% Ethylene Glycol I Monobutyl Erasile 4.5% Water 90qb Example 3 Nonionic surfactant of Synthesis Example 2 20 Cheyarol CT
-15-thiisopropyl alcohol 20% Water 55% Example 4 Nonionic surfactant of Synthesis Example 3 17% Eyarol CT
-13% ethylene glycol monobutyl ether 10% water 7
Comparative Example 1 Nonionic surfactant of Synthesis Example 1 30% ethylene glycol monobutyl ether water 45% Comparative Example 2 Poly(20) oxyethylene sorbitan trioleate 25% Yarrow Pre CT-1 5% ethylene glycol monobutyl ether 25% water 4
5% Example 1-4, Comparative Example 1.2, and flash point (JISK-2265), fish toxicity (TL
m24. JISK-0102), emulsification rate (according to the test method stipulated in the Ministry of Transport Chief Cabinet Secretary's Notification (February 2, 1970, Kansai No. 21) "Standards for Use of Spilled Oil Dispersants").

) and oil dispersibility test results are shown in Table 1.

The emulsification rate of the test method specified in the Ministry of Transport Chief Cabinet Secretary's Notice (hereinafter simply referred to as the Notice) is as follows: Emulsification width: 40cm, rotation speed: 30mm
Since the emulsification was performed under strong stirring by shaking vertically at 0 rpm for 5 minutes, the emulsifying property of the oil under weak stirring was investigated as oil dispersibility. The test method is the same as the test method specified in the notification.
Add 5 go. Add 2 d of oil on top of it, then add the spilled oil dispersant and let it stand for 1 minute, then drop 25111/l of seawater with a whole pipette from the top opening of the dropping funnel.After 30 seconds have passed after the dripping is finished, from the bottom. Seawater with oil dispersed 251
While thoroughly stirring 1j with a magnetic stirrer, accurately take 2014 out of this and measure the oil content in it. The oil content was measured using the same operating method as the test method specified in the notification, and the test results shown in Table 1 were obtained. The amount of spilled oil dispersant added when measuring the emulsification rate using the test method specified in the notification is 20% (Volume
i/VoluInII, but the emulsification rate and oil dispersibility in Table 1 were measured by varying the amount of spilled oil dispersant added. As is clear from Table 1, the spilled oil dispersant of the present invention has the same or better performance compared to currently commercially available spilled oil dispersants with a clearly smaller amount added, and in terms of fish toxicity, Table 1. Judging from the results of Test 1, the treatment of spilled oil with the spilled oil treatment agent of the present invention achieves the same or better performance than conventional products with a smaller amount added, so it is a non-polluting type of spilled oil that does not pollute the environment. It turns out that it is a processing agent.

Patent use person Toho Chemical Industry Co., Ltd.

Claims (1)

[Scope of Claims] (Part 41 - A polyoxyalkylene multi-bent alcohol polyfatty acid ester represented by the general formula and sodium dioctyl sulfosuccinate are blended in a weight ratio of 1.5:1 to 15=1. 2-60% by weight of surfactant, 0-5% of water-soluble solvent
A water-soluble oil spill dispersant characterized by comprising 0% by weight and 10-98% by weight of water (2) General formula: % A is an integer in the range of 3-6 The water-soluble oil spill treatment agent according to claim 1, which uses polyhydric alcohols such as glycerin, diglycerin, trimethylolpronogne, sorbitol, sorbitan, mannitol, and pentaerythritol. (3) General formula % Formula %) The water solubility according to claims 1 and 2, whose proportions are 50-90% by weight and 50-10% by weight, and the total number of moles added is 15-50. Mold spill oil treatment agent.