JPH0321305A - Oil-water separation agent - Google Patents

Abstract

PURPOSE:To prepare an oil-separation agent to be able to separate easily low grade oil content by addition polymerizing alkylene oxide with 12C or more carboxyl of higher polybasic acid having two or more of carboxyl radicals in a molecule. CONSTITUTION:An oil-water separation agent is prepared by using a surfactant, composed of alkylene oxide (for example, ethylene oxide or propylene oxide) addition polymerized with 12C or more carboxyl of higher polybasic acid (Saturated or unsaturated dibasic acid called dimer acid or saturated or unsaturated acid called trimmer acid can be used individually or as a mixture.) having two or more of carboxyl radicals in a molecule, as a main component. Oil-water separation can be carried out by using the surfactant added, stilled and mixed even with oil-water mixed liquid of low grade in which oil-water separation heretofore was not possible.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention is capable of separating oil and water from an oil/wood mixture even when the oil and water exist in the form of an emulsion or a particle dispersion. This article relates to an oil wood separating agent that can

<Prior art> Examples of cases in which oil and water exist in the form of an emulsion or a dispersion include emulsions that occur when heavy oil is washed with water for desalination, emulsions that occur when heavy oil is mixed with rainwater due to an accident, Emulsions produced when crude oil extracted from oil wells contains water; emulsions produced when crude oil is washed with water for desalination during crude oil refining; emulsions produced when crude oil and water are simultaneously transferred through a transport pipe; Emulsions are created when cutting oil and other oils flow into drainage water.

These emulsions include the W/O type, in which water is separated into oil, and the O type, in which oil is dispersed in water.
/W type, and physical methods such as heating or centrifugation are used as oil-water separation methods to break the above-mentioned emulsion and separate it into two layers of oil and water.

In addition, if the emulsion is stable or the amount of dispersoid is very small compared to the dispersion medium, an oil wood separating agent may be added.
The above-described chemical method is used in combination with the above-mentioned physical method.

For example, if there is more than 5% moisture in heavy oil as fuel oil, the combustion condition will become unstable when using a boiler burner, so according to JIS regulations, general heavy oil must have a moisture content of 2% or less. In addition, in crude oil refining, if there is too much water after desalting, it can cause tossing, which can damage the refining equipment. Therefore, it is necessary to separate the water in the oil by the method described above.

Conventional oil-water separation agents added to the emulsion solution as described above include polyoxyethylene alkyl allyl ether, polyoxyethylene alkyl amine, polyoxyethylene polyoxybrobylene block polymer,
Various surfactants are used, such as polyoxyethylene alkylphenol ether, polyoxyethylene polyoxypropylene, and alkylphenol ether. <
Problems to be Solved by the Invention> When the above-mentioned surfactants are added to an emulsion solution, they are placed at the interface between the oil phase and the aqueous phase, and are dispersed by a slight physical action such as stirring or heating. This method is used to separate oilwood by agglomerating it, but in recent years, with the decline in the quality of oil,
Even if the above-mentioned various surfactants are used, sufficient oilwood separation is not achieved, for example, even if the oilwood is separated into layers,
An oil phase containing water in the form of an emulsion often remains at the interface.

In addition, the oilwood separation effect is insufficient just by adding the above-mentioned surfactants, and it is often necessary to use physical methods such as centrifugation and heating in combination.Moreover, if the physical method is stopped after the oilwood separation, the oilwood separation effect is insufficient. often becomes an emulsion again. <Means for Solving the Problems> The present invention was proposed in view of the above, and as a result of intensive research aimed at developing a surfactant that is also effective for separating oil from low-grade oil, This paper proposes an oilwood separating agent whose main component is a surfactant obtained by addition-polymerizing alkylene oxide to the carboxyl group of a higher polybasic acid having 12 or more carbon atoms and containing 2 or more carboxyl groups. be. Conventionally, surfactants made by addition-polymerizing alkylene oxide to the carboxyl group of monobasic acids such as oleic acid, stearic acid, and lauric acid have been widely used as surfactants for emulsifying and dispersing purposes. However, these surfactants have no oil-water separation effect at all, not only with low-grade oils as mentioned above, but also with high-grade oils. In addition, in general, alkylene oxide having a large number of moles added is effective for oil wood separation, preferably 20 to
100 is said to be suitable, but even surfactants prepared by addition-polymerizing alkylene oxide to the carboxyl group of a monobasic acid within this range are only slightly effective in separating low-grade oils.

On the other hand, higher polybasic acids having 12 or more carbon atoms and containing two or more carboxyl groups in the molecule are reactive diluents for epoxy resins, curing agents for epoxy resins, curing agents for acrylic powder coatings, and polyamide resins. The oil-wood separation agent of the present invention is a high-grade ester obtained by addition-polymerizing alkylene oxide to the above-mentioned high-grade polybasic acid. It was discovered that the derivative exhibits an excellent ability to separate oil wood, and the present invention was completed. As the polybasic acid used in the present invention, saturated or unsaturated dibasic acids called dimer acids and saturated or unsaturated tribasic acids called trimer acids can be used alone or in mixtures. A long chain with 12 or more carbon atoms, or a derivative having an alkyl group or an aromatic ring side chain in the long chain, a dibasic acid with 36 carbon atoms obtained by polymerization of tall oil fatty acid, and a tribasic acid with 54 carbon atoms. Acids etc. can be used.

In the present invention, the main component of the oil-water separating agent is a surfactant obtained by addition-polymerizing alkylene oxide to the carboxyl group in the higher fatty acid molecule as described above.

Here, as the alkylene oxide, for example, ethylene oxide, brobylene oxide, etc. can be used.

In this case, the addition polymerization conditions include, for example, adding ethylene oxide, brobylene oxide, etc. to a higher polybasic acid at a reaction temperature of 80 to 160°C.

Regarding the form of the adduct, there are (a) one in which ethylene oxide is added, and (b) one in which brobylene oxide is added. In this case, the number of moles of ethylene oxide or brobylene oxide added is 2, respectively.
A suitable amount is about 0 to 120 moles, preferably about 30 to 80 moles.

On the other hand, in the combined addition of ethylene oxide and propylene oxide, (C) ethylene oxide is added and then brobylene oxide is added; (d) brobylene oxide is added and then ethylene and oxide are added. The number of moles of ethylene oxide or brobylene oxide added is 10, respectively.
Appropriate amounts are approximately 70 mol, preferably 20 to 50 mol each.

In addition, generally, the number of moles of alkylene oxide added to the higher polybasic acid is about 30 to 80 moles,
The molecular weight of the higher ester derivative obtained by this addition polymerization is 3000 to 900. It is preferable to set it to about 0.

The oil-water separating agent of the present invention has the above-mentioned higher ester derivatives as its main components, and these may be used alone or in a mixture of two or more. Further, it can be used by dissolving and diluting it in kerosene, methylnaphthalene, A heavy oil, ether alcohol such as butyl cellosolve, higher alcohol such as dovanol, water, or the like. Furthermore, the higher ester derivative according to the present invention may be used in combination with existing oilwood separation agents. The oil wood separating agent of the present invention can be applied to any liquid oil such as crude oil, refined oil, slop oil, tar, etc. These liquid oils and water are in an emulsion or dispersion state. Simply add it to the mixture. <Effects of the Invention> When the oil-wood separation agent of the present invention is mixed with a solution of oil and water in the form of an emulsion and sufficiently stirred, the emulsion is demulsified and the oil layer is on top and the water layer is on the top due to the difference in specific gravity. Separate below. In this case, follow? By using the oil-wood separation agent of the present invention, the oil-water interface becomes extremely clear, making it possible to easily separate even low-grade oils for which the surfactant described above is insufficiently effective.

In addition, the time required for oil-wood separation is extremely short, and emulsion is almost never re-formed after oil-water separation.

That is, the higher ester surfactant used in the present invention is different from conventional oil wood separation agents in that it has a special form in which it has two or more parent wood groups at the terminal or side chain of the higher lipophilic group. By optionally adding and polymerizing alkylene oxides such as ethylene oxide and brobylene oxide, the molecular weight can be increased, making it possible to separate low-grade oil and water, which was impossible to separate with conventional surfactants alone. Oil and water can be separated extremely easily, in a short time, and reliably by simply adding the oil and water to the mixture at night, stirring, and then combining.

<Example> Examples of the present invention will be shown below.

Reference Example 1 [Production of higher ester derivative (A)] C represented by HOO(:-(CHx)+.-COOH,
. Linear dibasic acid (C*o}IssOn. Molecular weight 3421
1 g of 342g% NaOH was added to the autoclave, and 100 mol of gaseous ethylene oxide was gradually introduced into the autoclave to effect addition polymerization of ethylene oxide to the dibasic acid at a reaction temperature of 140 to 160°C and a reaction pressure of 10 atm. After adding the entire amount of ethylene oxide, the reaction was continued by stirring the inside of the autoclave until the pressure stopped decreasing.

As a result of analysis of the reaction product, a higher ester derivative (A) was produced in which the average number of moles of ethylene oxide added to free carboxylic acid was 45 moles.

Reference Example 2 [Production of higher ester derivative (B)] 600 g of a compound of 80% C ia dibasic acid and 20% C 84 tribasic acid was used as the polybasic acid, and the synthesis procedure was as follows: ), a higher ester derivative (II) having an average number of added moles of ethylene oxide of 40 moles was produced.

Reference Example 3 [Production of higher ester derivative (C)] The synthesis procedure was carried out according to the above higher ester derivative (A), but propylene oxide was added instead of ethylene oxide, and addition polymerization was carried out using K01 as a catalyst. As a result of the reaction, a higher ester derivative (C) having an average number of added moles of brobylene oxide of 43 moles was produced.

Reference Example 4 [Production of higher ester derivative (D)] tL6c. represented by the following structural formula. ．． 438 g of dibasic acid (c2sns-o-, molecule full 438) and 2 g of KOII were added to the autoclave, and 70 moles of ethylene oxide was gradually introduced in gaseous form to carry out an addition polymerization reaction.

The reaction thirst, reaction pressure, and reaction end point were determined in the same manner as in the case of higher ester derivative (A), and after the reaction was completed, the pressure was reduced to remove unreacted ethylene oxide and the like.

Brobylene oxide was added to the obtained reaction product to carry out an addition polymerization reaction in the same manner as in the case of ethylene oxide.

As a result of the analysis, a higher ester derivative (D) was produced in which the number of added moles of ethylene oxide was 30 moles and the number of added moles of brobylene oxide was 32 moles.

Reference Example 5 [Production of higher ester derivative (E)] C sm dibasic acid (cssua4o-, molecular weight 560)
560g was used, and the synthesis procedure was performed using higher ester derivatives (
A higher ester derivative (E) containing 30 moles of ethylene oxide and 27 moles of brobylene oxide was produced by carrying out the procedure according to D).

Reference Example 6 [Production of higher esmel derivative (F)] C. Tribasic acid (Cs4H*60g, molecular weight 840) 8
Using 40g, the synthesis procedure is higher ester derivative (D)
The number of additions of brobylene oxide is 2.
A higher ester derivative (F) containing 2 moles of ethylene oxide and 22 moles of added ethylene oxide was produced.

The compositions of Examples 1 to 6, which are oilwood separation agents containing the above-mentioned higher ester derivatives (A) to (F) as main components, are shown below. Moreover, oil-water separation agents having compositions in which the above-mentioned higher ester derivatives are not added are shown as Comparative Examples 1 to 6.

Example 1 Higher ester derivative (A) 20wt% polyoxyethylene alkylphenol ether
20 Nono [Daiichi Kogyo Seiyaku (Noigen EAL40 made by Wiss)] Butyl cellosolve methyl naphthalene kerosene Example 2 Higher ester derivative (13) Butyl cellosolve methyl naphthalene kerosene 20 Nono 20 〃 20 〃 Example 3 Higher ester derivative (C) Butyl cellosolve methyl naphthalene kerosene Clen kerosene Example 4 Higher ester derivative (D) Butyl cellosolve methylnaphthalene kerosene Example 5 Higher ester derivative (E) Butyl cellosolve methyl naphthalene kerosene Example 6 Hebutadecenylhydrohydroxyhydroxyethyl isidazoline 35 wt% Higher ester derivative (F) Butyl Cellosolve 5 〃 20 Nonomethylnaphthalene Kerosene Comparative Example 1 Roth Oil Butyl Cellosolve Methyl Naphthalene Kerosene Comparative Example 2 Neugen EAl40 Butyl Cellosolve Methyl Naphthalene Kerosene Comparative Example 3 Tetronic Activator Butyl Cellosolve Methyl Naphthalene Kerosene Comparative Example 4 20 wt % 20 Formalin condensate of nonoborioxyethylene alkylphenol ether 4wt% Butyl cellosolve 20 wt% Methylnaphthalene 20 Kerosene
20//Comparative Example 5 Dioctyl sulfosarcinate 40 wt% butyl cellosolve 30 Kerosene
30 Comparative Example 6 Hebutadecenyl hydroxyethyl isidazoline 40 wt% butyl cellosolve 20 Methylnaphthalene 20 Kerosene
20〃 (Evaluation method 1) The oilwood separation agents of Example 1.2 and Comparative Example 1.2 described above were individually added to heavy oil containing 50% by volume of water in the form of an emulsion.
ppm, stir thoroughly for 1 minute, and then add 100+el
(Contains approximately 50ml of water. Contains approximately 50+wl of heavy oil)
The sample was collected in a graduated cylinder and placed in a constant temperature water bath at 80°C. Separated water after 10 minutes, 30 minutes, 1, 2, and 4 hours after standing still! (+al) is shown in Table 1.

No. l table Table 2 shows the amount of water separated (+nl) at the time.

Table 2 (Evaluation Method 2) Add 10 ml of water to 90 ml of Minas crude oil and mix at 3500 r.p.m.
p. A large number of crude oil emulsions were prepared by stirring thoroughly for 1 minute using a homogenizer rotating at m. To this crude oil emulsion were added 10 pp of each of the separating agents of Examples 3 to 6.
After stirring for 30 seconds, 100 ml of the solution was placed in a centrifuge tube and placed in a constant water bath at 80°C.

Procedural amendments after 10 minutes, 30 minutes, 1 hour, and 2 hours have passed after standing still (voluntary) April 12, 2017

Claims (1)

[Claims] Contains 2 or more carboxyl groups in the molecule and has 1 carbon number
An oil-water separating agent whose main component is a surfactant obtained by addition-polymerizing alkylene oxide to the carboxyl group of a higher polybasic acid of 2 or more.