JPS6035392B2 - Composition for organic matter recovery - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a composition for recovering organic matter that forms an oil layer on water by turning it into an oil-collecting gel, and more specifically, for recovering organic matter that forms an oil layer on water, and more specifically, for recovering organic matter that forms an oil layer on water. The present invention relates to a composition that converts oil or an oil film spilled onto water into an oil collecting gel and recovers the oil components.

There are many cases where oil spills onto the sea or river water due to accidents during ship navigation, protective operations during oil transfer, oil films caused by ballast water, tank damage, etc. Such oil spills cause serious social problems such as damage to marine products due to water pollution, river pollution, damage to fishermen and residents, fear of fire outbreaks, and environmental destruction. Therefore, various measures have been taken and researched and developed to recover the spilled oil. The main methods used for this purpose include the combination of oil fences and adsorption mats, and the use of emulsifying and dispersing agents, but these methods are still far from satisfactory. That is, it is impossible to use an oil fence, for example, on the open ocean far from the coast, and it is not practical except in special cases. The use of adsorption mats involves considerable danger and difficulty when dealing with oils that are highly ignitable and flammable, and there are limits to what they can adsorb. Furthermore, the use of emulsifying and dispersing agents cannot prevent pollution of the sea, coasts, etc. The present inventors have previously developed a method for separating organic substances from a mixture of water and organic substances using penzylidene sorbitol (Samuraiko Sho 49-72 issue). In this method, the penzylidenesorpitol described above gels (solidifies) by dissolving in oil.
Utilizing this mechanism, the hydrophilic solvent solution of penzylidenesorpitol is used as an oil-water brood agent to solidify and separate the oil from the aqueous phase. The above-mentioned solvent solution is effective for recovering organic matter, but the gelled recovered oil obtained by using it contains approximately the same amount to about 5 times the amount of water as the oil content, and the oil content due to its use is There was still room for improvement in recovery efficiency. In view of the above-mentioned current situation, the present inventors have continued to conduct various studies, and have found that it is possible to reduce the oil film formed on water, and to selectively gel and recover only the oil film, thereby substantially removing water. The present inventors have discovered a new composition for gelling and recovering organic substances that does not contain water and has a good so-called watering property, and has now completed the present invention.

That is, the present invention provides an organic matter recovery composition for gelling and recovering organic matter that forms an oil layer on water, wherein the composition has the following general formula (1) [wherein R is a hydrogen atom, a halogen atom, or a lower alkyl group] , a lower alkoxy group or a nitro group, and p indicates 0 or 1] (hereinafter referred to as component 1) 1 to 9% by weight; (0) a hydrophilic solvent that is a good solvent for the above component (hereinafter referred to as component 0); ) 15 to 70% by weight,
(Dish) A hydrophobic solvent with a solubility in water of 5 or less (hereinafter m −
at least one solvent selected from the group consisting of cyclohexanone, alkylcyclohexanone, N-cyclohexy-2-pyrrolidone, and N-alkyl-2-pyrrolidone (hereinafter referred to as m-b component);
(hereinafter referred to as m component) 15 to 8% by weight, (N)
Polybutene oligomer, polybutadiene oligomer, polyester oligomer, Jen-based oligomer having a hydroxyl group, carboxyl group, halogen atom or amino group as a functional group at the molecular end, vinyl ether oligomer, acrylate oligomer, methacrylate oligomer, liquid polyether, liquid polyester, 1 to 30% by weight of an oligomer or polymer selected from petroleum resin, hydroxypropyl cellulose, methyl cellulose, and atactic polypropylene (hereinafter referred to as W component), and optionally (V) surfactant (hereinafter referred to as V component) 1 weight % or less.

Based on the fact that the composition of the present invention is composed of specific amounts of the above-mentioned components 1 to V, it selectively collects and solidifies the organic oil film formed on water such as water spill oil, and separates and recovers the oil from the water. Make it easier.

In particular, the selectivity of oil gelation by the composition of the present invention is very high, and it is possible to make the water content of the gelled product practically nonexistent. Furthermore, the composition of the present invention exhibits a homogeneous liquid state itself, and can be easily applied to water oil by spraying, etc., so that the water oil can be quickly and uniformly gelled in a short period of time. It has the advantage that there is no risk of remaining fossilized oil. Furthermore, the gelled oil obtained by the above method has a concentration of about 100 to 7
It has a gel strength of 0.00 kg/m, and is easy to drain, so it can be easily collected using a net from, for example, a towing boat, and the recovered gelled oil can be easily recovered by simple operations such as dilution and distillation. Can be used for playback. The organic matter to be gelled and recovered by the composition of the present invention is not particularly limited and includes all organic matter as long as it forms an oil layer or oil film on water.

Typical examples include crude oil, heavy oil, naphtha, kerosene, various phthalates such as DOP and DHP, lubricating oils, higher alcohols, gasoline, ethyl acetate, benzene, toluene, xylene, alkylbenzene, aniline, paraffin, Q-olefin, Examples include various epoxides, phenols, organic halides, nitrides, animal and vegetable oils, amines, nitriles, ketones, animal and vegetable oil methyl esters, oily polymer solutions, and emulsions thereof. The above general formula [1] used as one component in the present invention
Examples of the compound represented by the formula include various known penzylidene sorbitols and penzylidene xylitols. These can be used alone or in combination of two or more. Suitably, the amount used is about 1 to 9% by weight, preferably about 3 to 9% by weight. As the hydrophilic solvent used as the zero component, any of the various ones conventionally known as good solvents for the first component can be used.

Representative examples include N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, ethylene carbonate, sulfolane, methyl cellosolve, ethyl cellosolve, N-methyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N,N- Examples include -dimethylaminopropylmethacrylamide, N-isobutoxymethylacrylamide, N,N-dimethylacrylamide, and N-vinyl-2-pyrrolidone, which can also be used singly or in combination of two or more.
The amount used is about 15-7% by weight, preferably about 20% by weight.
~65% by weight. In the composition of the present invention, it is essential to further blend a melon component, a W component, and a V component according to the specifications in addition to the above-mentioned components 1 and 2, thereby achieving the excellent effects desired by the present invention.

The above m component is a hydrophobic solvent (m-
component a) and a specific solvent (component m-b) consisting of cyclohexanone, alkylcyclohexanone, N-cyclohexy-2-pyrrolidone, and N-alkyl-2-pyrrolidone
It can be broadly classified into. Examples of the m-a component include the following various compounds. <m-a component>{1' Alcohols having 6 to 20 carbon atoms hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, dodecyl alcohol, tetradecyl alcohol, hexadecyl alcohol, octadecyl alcohol, oleyl alcohol, eicosyl alcohol, C, 6-2o dimerized alcohol, etc.

(2} Hydrocarbons having 10 to 50 carbon atoms Decane, dodecane, tridecane, tetradecane, bentadecane, hexadecane, octadecane, eicosane, 1-decene, 1-
Dodeceso, 1-undecene, 1-tetradecene, 1-pentadecene, 1-octadecene, 1-eicosene, etc., and low polymers such as olefins having 2 to 20 carbon atoms, butadiene, isoprene, etc.

'3} C 6-40 esters stearyl stearate, oleyl stearate, butyl stearate, octyl stearate, octyl benzoate, ethylene glycol distearate, propylene glycol distearate, dioctyl adibate, dioctyl sebacate , dioctyl azelate, dioctyl maleate, monoglyceride, diglyceride, dioctyl phthalate, dibutyl phthalate, dihexyl phthalate, diisodecyl phthalate, dinonyl phthalate, oleyl oleate, methyl benzoate, methyl stearate, ethyl stearate, dioctyl tetrahydrophthalate, dioctyl hexahydro Low polymers such as phthalate, dibutyl succinate, and acrylate and methacrylate.

■C10-30 ethers dioctyl-7yl, triisobutylidene sorbide,
Dimyristyl ether, myristyl octyl ether, etc.

'5) Epoxy compounds having 10 to 56 carbon atoms Corresponding Q-olefin epoxide, epoxidized linseed oil, epoxidized soybean oil, epicote 828 cyclohexene oxide, epoxidized oleyl alcohol, epoxidized tung oil, epoxidized oleyl Lusterate et al.

6 Vegetable oils such as coconut oil, soybean oil, linseed oil, tung oil, liquid palm oil, rapeseed oil, etc.

{71 Alkyl halides having 1 to 20 carbon atoms, such as chloroform, tetrachloroethane, dichloroethane, dibromethane, etc.

■ Carboxylic acids with 6 to 50 carbon atoms, isostearic acid, nonanoic acid, decanoic acid, oleic acid,
dimer acid etc.

Among these, (1) alcohols, '5) epoxy compounds and (2) vegetable oil are preferred.

Also, an alkyl group that constitutes the dish-b component.

Examples of hexanone include those having an alkyl group having 1 to 8 carbon atoms, such as methylcyclohexanone, ethylcyclohexanone, butylcyclohexanone, hexylcyclohexanone, etc.; as N-alkyl-2-pyrrolidone,
Those having an alkyl group having 4 to 18 carbon atoms, such as N-butyl-2-pyrrolidone, N-hexyl-2-pyrrolidone, N-octyl-2-pyrrolidone, N-decyl-2-pyrrolidone, N-tetradecyl-2-pyrrolidone, N-tetradecyl-2-pyrrolidone, Examples include -hexadecyl-2-pyrrolidone. Among the m-b components, cyclohexanone is particularly preferred. The m-a component and m-b component may be used alone or in combination of about 15 to 8% by weight, preferably about 20 to 7% by weight.
It is used in a range of 5% by weight. A particularly preferred amount of the m-a component used is in the range of about 20-70% by weight, and that of the m-b component is in the range of about 30-75% by weight. This is m
-a component and m-b component (m component), when used in appropriate amounts, have the effect of collecting an oil film on water, preventing the transfer of one component to the aqueous phase, and gelling only the oil component. It has the effect of improving oil drainage. Especially 1
Since the component has no solubility in water, it is thought that if a drug containing a hydrophilic solvent and spilled oil come into contact with water after being mixed, gelation will gradually proceed from the interface. In any case, if component m is not used, or if it is used, it is used in an amount of 15% by weight or less, the selectivity of oil gelation will decrease when the resulting composition is used for gelation recovery of water oil. This is not preferable since the gelled product contains a relatively large amount of water. On the other hand, when using more than 8% by weight,
The resulting composition becomes gel-like and cannot maintain its liquid state, making it difficult to use. When an oil component is recovered using the composition of the present invention, the W component can particularly impart hardness (adhesive force) to the gelled oil obtained so that it cannot be easily disintegrated by a dispersion force below a certain level.

Any W component can be used as long as the composition maintains uniformity even when mixed. Especially 20oo
Preferably, a liquid with a viscosity of 50 ratio p or more,
Specific examples thereof include polybutene oligomers, polybutadiene oligomers, polyester oligomers, hydrogen-based oligomers having functional groups such as hydroxyl groups, carboxyl groups, halogen atoms, and amino groups at the molecular ends, vinyl ether oligomers, acrylate oligomers, and methacrylates. Examples include oligomers and oligomers such as liquid polyether, liquid polyester, and the like. In addition, the above N component includes petroleum resin, hydroxypropyl cellulose,
Solid resins such as methyl cellulose and atactic polypropylene can also be used, and these can be easily blended into a homogeneous composition, preferably by heating and mixing with a suitable solvent. The amount of the above W component to be used may be appropriately determined depending on the type and amount of other components used together with the N component itself, but if it exceeds 3% by weight in the total composition. When used, the viscosity of the composition becomes too high, resulting in poor handling properties, which is undesirable. Usually, the W component is preferably blended in a range of 1 to 2% by weight, thereby achieving the desired effect. In addition, component V, which is optionally blended into the composition of the present invention, may be separated depending on the combination of component (b) and component (m) described above during gelation of water oil by the resulting composition. It also has the effect of reducing the water content in gelled oil.

As the V component, conventional nonionic, anionic, and amphoteric surfactants can be used, and among them, nonionic surfactants, specifically sorbitan monoalkyl surfactants such as sorbitan monooleate and sorbitan monostearate, can be used. Sorbitan trialkyl esters such as ster, sorbitan triolate, and sorbitan tristearate, ethylene oxide adducts of higher saturated and unsaturated alcohols, monoglycerides, diglycerides, polyoxyethylene alkylamides, polyoxyethylene alkyl esters, soaps, Higher alcohol sulfate ester salt,
Higher alcohol ether sulfate ester salts and the like are preferred.
These V components are used singly or in combination of two or more, usually in a range of up to about 10% by weight, preferably about 0.2 to 5% by weight, more preferably about 0.5 to 3% by weight. It will be done. The composition of the present invention is prepared by simply mixing predetermined amounts of the components 1 to V described above.

The above-mentioned mixing can be carried out by a normal rope scouring operation, and a slight heating operation may be employed to achieve uniform mixing in a shorter time. The composition of the present invention thus obtained is used by spraying an appropriate amount onto the oil or oil film to be treated on water, similarly to known compositions for recovering organic matter of this type.

The amount of spraying varies slightly depending on the type and amount of each component making up the composition and the type of oil to be treated, and can be determined appropriately, but usually when treating heavy oil, crude oil, animal and vegetable oils, etc.
About 10-6% by volume, preferably about 15-6% by volume for these
It is optimal to set the volume to 4%, and naphtha, kerosene,
About 10-2% by volume is sufficient for toluene and the like. By applying the above-mentioned composition of the present invention, water oil is quickly and completely gelled (solidified), and the resulting gelled oil contains almost no water and is strong and has good drainage properties. . Therefore, it can be subsequently very easily collected using a net from a towing vessel, and the oil content can be regenerated from the gelled oil thus collected by appropriate means such as dilution and distillation. As described above, the present invention provides an effective and economical composition and method that can selectively recover only the oil by gelling an oil film of organic matter formed on water such as water spill oil. This is an extremely effective new technology for dealing with the oil spills that have become a problem.

Examples and comparative examples will be given below to explain the present invention in more detail.

Example 1 Dibenzylidene sorbitol 3% by weight N,N-
Dimethylacetamide 20 Cyclohexanone
70 Polypden (number average molecular weight 1500) 7 The above four compounds are mixed under 3500 to obtain the composition of the present invention.

On the other hand, 500 g of seawater was put into a 1 x 1 x 1 aquarium, 5 g of heavy oil A was poured into it, and 1.5 g of the composition of the present invention prepared above was poured into it.

The mixture was mixed with a pestle blade for 5 minutes at the constant rotational speed shown below, left to stand for 2 minutes, and then the gelled oil produced was scooped out with a net with a diameter of 2 ribs, and its hardness, water content, and oil recovery rate were evaluated. Measure. The hardness can be determined by applying a round rod with a surface area of 1 to the gel at a loading rate of 10 mm/sec, and determining the weight percent (cm/cm) when the gel collapses.
The water content (%) was determined by the Karl Fischer method, and the oil recovery rate was determined by the following formula. Gelation curve (weight) Oil recovery rate (%) = used composition Q weight) 10 spilled oil (weight) x 100 For comparison, a composition prepared in the same manner using 70% by weight of cyclohexanone without adding the above polybutene was prepared. The same test was repeated using

The results obtained are shown in Table 1 below for comparison.

Table 1 As shown in Table 1 above, the composition of the present invention does not disintegrate the gel even when subjected to considerably high speed (15 pm) nada grouping during oil recovery, as in the case of low speed simulated azusa, and can be easily and reliably coated with a net. It can be seen that gelled oil can be recovered.

On the other hand, in the case of the comparative composition, under the above-mentioned Takato rope conditions, a portion of the gel once formed collapses and becomes paste-like.
It can be seen that this makes online collection difficult and reduces the collection rate. The gelled oil recovered by using the composition of the present invention was a plate-shaped gel block. Comparative Example 1 Dibenzylidene sorbitol 15% by weight N,
N-Dimethylacetamide 85 A comparative composition is prepared by mixing the above two types at room temperature.

Into the same water tank as in Example 1 containing 500 g of seawater, 5 g of heavy oil A was poured, and 2 g of the above comparative composition was poured therein, and 30 minutes later, formation of gelled oil was observed.

As a result, heavy oil A was partially gelled to a small extent, but mainly only the water layer was observed to be gelled. Example 2 Dibenzylidene xylitol 5% by weight N-methyl-2-pyrrolidone 60 Dioctyl maleate 14 ″terminal hydroxy polybutadiene 20 (molecular weight 2000) Polyoxyethylene lauryl alcohol ether 1
(Number of moles of ethylene oxide added: 5) The above five types are mixed at room temperature to obtain the composition of the present invention.

Separately, for comparison, a composition consisting of four types of compounds (however, the amount of dioctyl maleate was 34% by weight) was obtained without using the terminal hydroxy polybutadiene.

Table 2 below shows the results of repeating the same test as in Example 1 using each of these and adopting a speed condition of 15 pm.

Table 2 It can be seen from the above Table 2, as in Table 1, that by using the composition of the present invention, gelled oil can be easily and reliably recovered using a net.

Example 3 Dimethylbenzylidene sorbitol 4% by weight dimethyl sulfoxide 40 N,N-dimethylformamide 10 Decyl alcohol
30″ methyl pinylether oligomer
10 Sorbitan monostearate (molecular weight 3000) 6 The above six types are mixed at room temperature to obtain the composition of the present invention.

Separately, for comparison, a comparative composition was obtained in the same manner as above except that the methyl vinyl ether oligomer was removed and decyl alcohol was used in an amount of 4% by weight.

Using each composition, an oil recovery test similar to that in Example 1 was conducted using white kerosene instead of heavy oil A and at a speed of 15 pm. The results obtained are shown in Table 3 below. Table 3 As with Tables 1 and 2, it can be seen from Table 3 that white kerosene can be easily and reliably recovered by using the composition of the present invention.

Example 4 Composition sample No. 4 of the present invention was prepared in the same manner as in Example 1 using each component listed in the fourth notation below. I got a score of 1-10.

Table 4 Each abbreviation in Table 4 indicates the following.

<1 component> DBS...Dibenzylidene sorbitol (1,3:2,4 combined) Me-DBS. ...G(p-methylbenzylidene)sorbitol Cso-D...G(p-chlorobenzylidene)sorbitol Me-DBX...
... Di(p-methylbenzylidene)xylitol E
t-D Already...G (p-ethylbenzylidene)
Sorbitol Me○-DBS... Di(p-methoxybenzylidene) Sorbitol <0 component> DMAc
・・・・・・N. N-dimethylacetamide NMP
...N-methyl-2-pyrrolidone NPP.・・・
．．・・N-propyl-2-pyrrolidone DMF. ．． ．．
．． ．． ．． N. N-dimethylformamide DMA ・. ．．・
...N. N-dimethylacrylamide DMSO...
・Dimethyl sulfoxide Using each of the samples (sample arms 1 to 10) shown in Table 4 above, a recovery test for heavy oil A was conducted in the same manner as in Example 1, and the hardness and water content of the gelled oil obtained were determined. When the oil recovery rate and oil recovery rate were measured, almost the same results were obtained.

That is, it has been confirmed that by using the composition of the present invention, spilled oil can be recovered very advantageously regardless of the number of flocs and therefore the actual wave conditions at sea or the like. Reference Example p-hydroxybenzaldehyde was used at a ratio of 1 mole to 1 mole of penzaldehyde, and the molar ratio of the total amount of penzaldehyde and p-hydroxybenzaldehyde used to sorbitol was 2:1. Comparative agent A is obtained by reaction, neutralization, and purification using solpitol in the presence of an acid catalyst in a conventional manner.

Further, comparative gelling agents B and C are obtained in the same manner as above except that 0.5 mol or 0.3 mol of p-hydroxybenzaldehyde is used per 1 mol of benzaldehyde.

Furthermore, dibenzylidene sorbitol, which is a gelling agent of the present invention, is obtained in the same manner as above except that only benzaldehyde is used and p-hydroxybenzaldehyde is not used.

This will be referred to as gelling agent D. Using the above-mentioned gelling agents A to D, four types of organic matter recovery compositions having the following compositions are obtained.

Gelling agent 4% by weight N,N-dimethylacetamide 26 Cyclohexanone
66 ″Polybutene (number average molecular weight 1500) 4″ Heavy oil A was gelled and recovered in the same manner as in Example 1 except that the obtained composition was used.

The recovery rate is as follows. Table 5 Gelling agent used A B C ○ Recovery rate (%) 45 50 80 99 As is clear from these results, the gelling agent was obtained by reacting p-hydroxybenzaldehyde and penzaldehyde together with sorbitol. It can be seen that when using the comparative gelling agents A to C, the oil recovery rate was low.

Claims (1)

[Claims] 1. An organic matter recovery composition for gelling and recovering organic matter that forms an oil layer on water, wherein the composition is
General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R represents a hydrogen atom, a halogen atom, a lower alkyl, a lower alkoxy group, or a nitro group, and p represents 0 or 1]
1 to 9% by weight of a compound represented by II, 15 to 70% by weight of a hydrophilic solvent that is a good solvent for the above component I, III, a hydrophobic solvent with a solubility in water of 5 or less, and cyclohexanone,
Alkylcyclohexanone, N-cyclohexyl-2-
15 to 80% by weight of at least one solvent selected from the group consisting of pyrrolidone and N-alkyl-2-pyrrolidone
. IV polybutene oligomer, polybutadiene oligomer, polyester oligomer, diene oligomer having a hydroxyl group, carboxyl group, halogen atom or amino group as a functional group at the molecular end, vinyl ether oligomer,
Acrylate oligomer, methacrylate oligomer,
It is characterized by consisting of 1 to 30% by weight of an oligomer or polymer selected from liquid polyether, liquid polyester, petroleum resin, hydroxypropylcellulose, methylcellulose and atactic polypropylene, and optionally 10% by weight or less of V surfactant. A composition for recovering organic matter. 2 Component II is N,N-dimethylformamide, N,N
-dimethylacetamide, dimethyl sulfoxide, ethylene carbonate, sulfolane, methyl cellosolve, ethyl cellosolve, N-methylpyrrolidone, N-propyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,
N-dimethylacrylamide, N-vinylpyrrolidone,
A composition according to claim 1 selected from N,N-dimethylaminopropylmethacrylamide and N-butoxymethylacrylamide. 3. The composition according to claim 1, wherein component III is a hydrophobic solvent having a solubility in water of 5 or less. 4 A hydrophobic solvent with a solubility in water of 5 or less has a carbon number of 6 to 2
0 alcohols, hydrocarbons with 10 to 50 carbon atoms, esters with 6 to 40 carbon atoms, ethers with 10 to 30 carbon atoms, epoxy compounds with 10 to 56 carbon atoms, vegetable oils, hydrocarbons with 1 to 20 carbon atoms Alkyl halide and carbon number 6-50
The composition according to claim 3, wherein the composition is selected from carboxylic acids. 5. The composition of claim 1, wherein component III is selected from cyclohexanone, C_1-C_8 alkylcyclohexanone, N-cyclohexyl-2-pyrrolidone and N-C_4-C_1_8 alkyl-2-pyrrolidone. 6. The composition according to claim 1, wherein the surfactant is a nonionic surfactant, an anionic surfactant, or a zwitterionic surfactant. 7 I component 3-9% by weight, II component 20-65% by weight, II
A composition according to claim 1, comprising 20 to 75% by weight of component I, 1 to 20% by weight of component IV and 0.5 to 3% by weight of component V.