JP2844470B2 - Oil-water separation agent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial application field> The present invention is to separate oil and water from an oil-water mixture even when the oil and water are present in the form of emulsion or particles. Oil-water separator.

<Conventional technology> When the oil and water are present in an emulsion state or a dispersion state, for example, an emulsion generated when heavy oil is washed with water to desalinate, an emulsion when rainwater or the like is mixed with heavy oil by accident, Emulsion when water is mixed in crude oil extracted from oil well, emulsion generated by washing with water for desalination during crude oil refining,
Emulsions generated when crude oil and water are simultaneously flowed and transported through a transport pipe, and emulsions generated when cutting oil and other oil components flow into drainage, and the like.

These emulsions have a W / O type in which water is dispersed in oil and an O / W in which oil is dispersed in water.
There is a type, and a physical method such as heating or centrifugation is used as an oil-water separation method for breaking the above-mentioned emulsion and separating it into two layers of oil and water.

When the emulsion is stable or the dispersoid is very small compared to the dispersion medium, an oil-water separating agent is added, and the above-described chemical method is used in combination with the above-described physical method. You.

For example, if 5% or more of moisture is present in fuel oil as a fuel oil, the combustion state is usually unstable when a boiler burner is used. It is stipulated that, even in crude oil refining, if there is a lot of water after desalting, topping may occur and the refining equipment may be damaged.In such a case, the emulsion has a very stable water content in the oil. Since it is present, it is necessary to separate the water in the oil by the method as described above.

Conventional oil / water separating agents to be added to the emulsion solution as described above include polyoxyethylene alkyl allyl ether, polyoxyethylene alkylamine, polyoxyethylene polyoxypropylene block polymer, polyoxyethylene alkylphenol ether,
Various surfactants such as polyoxyethylene polyoxypropylene alkylphenol ether are used.

<Problems to be Solved by the Invention> When the above-mentioned surfactant is added to the emulsion solution, it is arranged at the interface between the oil phase and the aqueous phase, and dispersed by a slight physical action such as stirring and heating. Although oil and water are separated by aggregating the quality, in recent years, with the deterioration of oil quality, even if the above various surfactants are used, sufficient oil / water separation is not performed. Even in this state, an oil phase containing water in an emulsion state often remains at the interface.

In addition, the oil-water separation effect is insufficient only by adding the above-mentioned surfactant, and it is often necessary to use a combination of physical methods such as centrifugation, heating, and the like. Are often emulsified again.

<Means for Solving the Problems> The present invention has been proposed in view of the above, and as a result of intensive research for the purpose of developing a surfactant which is also effective for oil-water separation of low-grade oil, has been developed as a result. It contains two or more carboxyl groups and has a carboxyl group of a higher polybasic acid having 12 or more carbon atoms, and proposes an oil / water separating agent mainly composed of a surfactant obtained by addition-polymerizing an alkylene oxide. is there.

Conventionally, surfactants obtained by addition-polymerizing an alkylene oxide to a carboxyl group of a monobasic acid such as oleic acid, stearic acid, and lauric acid have been widely used as surfactants for emulsification and dispersion. However, these surfactants have no oil-water separation effect at all even for high-grade oils as well as for low-grade oils as described above.

In general, the oil-water separation is effective when the addition mole number of the alkylene oxide is large, and preferably 20 to
Although it is said that 100 is suitable, even a surfactant obtained by addition-polymerizing an alkylene oxide to the carboxyl group of a monobasic acid as described above has only a slight effect on oil-water separation of low-grade oil.

On the other hand, higher polybasic acids having 12 or more carbon atoms containing two or more carboxyl groups in the molecule are reactive diluents for epoxy resins, epoxy resin hardeners, hardeners for acrylic powder coatings, and hot resins for polyamide resins. Although known for uses such as melt adhesive raw materials, plasticizers, lubricating oils, and rust inhibitors, the oil-water separator of the present invention relates to a higher ester derivative obtained by addition-polymerizing an alkylene oxide to the higher polybasic acid described above. The present inventors have found that they exhibit an excellent oil-water separation function, and have completed the present invention.

As the polybasic acid used in the present invention, a saturated or unsaturated dibasic acid called dimer acid or a saturated or unsaturated tribasic acid called trimer acid can be used alone or as a mixture. And a long chain having 12 or more carbon atoms, or a derivative having a side chain of an alkyl group or an aromatic ring in this long chain, and a dibasic acid having 36 carbon atoms and a tribasic having 54 carbon atoms obtained by polymerization of tall oil fatty acid Acids and the like can be used.

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

Here, as the alkylene oxide, for example, ethylene oxide, propylene oxide, or the like can be used.

In this case, the method of synthesizing the ester type surfactant is as follows.
As the conditions for addition polymerization, for example, ethylene oxide, propylene oxide
C. and a method obtained by esterifying polyhydric alcohols such as polyethylene glycol, polypropylene glycol, block copolymers of polyethylene glycol and polypropylene glycol, prolonic type, and higher fatty acids with a specified number of moles at a reaction temperature of .degree. And two kinds are generally performed. In this case, the esterification reaction is generally performed at 120 to 160 ° C. to remove water as a reaction product.

The form of the adduct may be (a) the addition of ethylene oxide or (b) the addition of propylene oxide when added alone. In this case, the added mole number of ethylene oxide or propylene oxide is respectively
20 to 120 mol, preferably about 30 to 80 mol is appropriate.

On the other hand, in the combined addition of ethylene oxide and propylene oxide, (c) ethylene oxide is added,
Followed by the addition of propylene oxide, (d)
There are those in which propylene oxide is added followed by ethylene oxide, and the number of moles of ethylene oxide or propylene oxide added is 10 to
70 mol, preferably about 20 to 50 mol, respectively.

Generally, the number of moles of the alkylene oxide added to the higher polybasic acid is about 30 to 80 moles, and the molecular weight of the higher ester derivative obtained by the addition polymerization is preferably about 3,000 to 9000.

The oil / water separating agent of the present invention contains the above-mentioned higher ester derivative as a main component, and these may be used alone or as a mixture of two or more. Further, it can be used by dissolving and diluting it in kerosene, methylnaphthalene, heavy oil A, ether alcohols such as butyl cellosolve, higher alcohols such as dovanol, water and the like. Further, the higher ester derivative according to the present invention may be used in combination with an existing oil / water separating agent.

The oil-water separator of the present invention can be applied to any oil as long as it is liquid, such as crude oil, refined oil, slop oil, and tar, and these liquid oils and water are in an emulsion or dispersion state. What is necessary is just to add to a liquid mixture.

<Effect of the Invention> When the oil-water separating agent of the present invention is mixed with a solution in which oil and water are in the form of an emulsion and sufficiently stirred and mixed, the emulsion is emulsified and destroyed. Separate below. In this case, the oil-water interface becomes extremely clear and can be easily separated by using the oil-water separating agent of the present invention, even with a low-grade oil that can only exert an insufficient effect with the conventional surfactant. Becomes

Further, the time required for oil-water separation is extremely short, and after the oil-water separation, there is almost no re-emulsification.

That is, the higher ester surfactant used in the present invention has a special form having two or more hydrophilic groups at the terminal or side chain of the higher lipophilic group, unlike the conventional oil / water separator, and ethylene oxide, Since the molecular weight can be increased by arbitrarily addition-polymerizing an alkylene oxide such as propylene oxide, the oil-water mixture of low-grade oil and water, which cannot be separated with conventional surfactants alone, cannot be used. The oil-water separation can be performed very simply, in a short time, and surely by simply adding and stirring and mixing.

<Examples> Examples of the present invention will be described below.

Reference Example 1 [higher ester derivative (A) preparation of] HOOC- (CH _{2) 18} C ₂₀ straight-chain dibasic acid represented by _{-COOH (C 20 H 38 O 4} , molecular weight 342) 342 g, the NaOH1g autoclave Further, 100 mol of gaseous ethylene oxide was gradually passed through, and ethylene oxide was addition-polymerized to dibasic acid at a reaction temperature of 140 to 160 ° C. and a reaction pressure of 10 atm. After the total amount of ethylene oxide was added, the reaction was carried out by continuously stirring the inside of the autoclave until the pressure did not decrease.

As a result of analyzing the reaction product, a higher ester derivative (A) having an average of 45 moles of ethylene oxide added to the free carboxylic acid was produced.

Reference Example 2 C ₃₆ 80% dibasic acid as a polybasic acid Production of higher ester derivative (B)], using a mixture 600g of 20% C ₅₄ tribasic acid, synthetic steps to the higher ester derivative (A) According to the same procedure, a higher ester derivative (B) having an average number of moles of added ethylene oxide of 40 mol was produced.

Reference Example 3 [Production of Higher Ester Derivative (C)] The synthesis procedure was the same as that for the above higher ester derivative (A), except that propylene oxide was added instead of ethylene oxide, and KOH was used as a catalyst to carry out the addition polymerization reaction. As a result, a higher ester derivative (C) having an average number of moles of added propylene oxide of 43 mol was produced.

Reference Example 4 [Production of higher ester derivative (D)] The following structural formula In C ₂₈ dibasic acids (C ₂₈ H ₃₈ O _4, molecular weight 438) represented 438g and K
2 g of OH was added to the autoclave, and an addition polymerization reaction was carried out by gradually passing 70 mol of ethylene oxide in gaseous form.

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

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

As a result of the analysis, a higher ester derivative (D) having an addition mole number of ethylene oxide of 30 moles and an addition mole number of propylene oxide of 32 moles was produced.

Reference Example 5 [higher esters preparation of derivatives (E)] C ₃₆ dibasic acids (C ₃₆ H ₆₄ O _4, molecular weight 560) was used 560 g,
The synthesis procedure is performed according to the higher ester derivative (D),
A higher ester derivative (E) having an addition mole number of ethylene oxide of 30 moles and an addition mole number of propylene oxide of 27 moles was produced.

Reference Example 6 [higher esters preparation of derivatives (F)] C ₅₄ tribasic acid (C ₅₄ H ₉₆ O _6, molecular weight 840) was used 840 g,
The synthesis procedure is performed according to the higher ester derivative (D),
A higher ester derivative (F) having an addition mole number of propylene oxide of 22 moles and an addition mole number of ethylene oxide of 22 mole was produced.

Each of the above-mentioned higher ester derivatives (A) to (F)
The compositions of Examples 1 to 6, which are oil / water separating agents containing as a main component, are shown. In addition, the oil-water separator having the composition without the above-mentioned higher ester derivative was shown as Comparative Examples 1 to 6.

Example 1 Higher ester derivative (A) 20 wt% polyoxyethylene alkyl phenol ether 20 [Neugen EA140 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.] Butyl cellosolve 20 methyl naphthalene 20 kerosene 20 Example 2 Higher ester derivative (B) 40 wt% butyl cellosolve 20〃 methyl naphthalene 20〃 kerosene 20〃 Example 3 Higher ester derivative (C) 40 wt% butyl cellosolve 20〃 methyl naphthalene 20〃 kerosene 20〃 Example 4 Higher ester derivative (D) 40 wt% butyl cellosolve 20〃 methyl naphthalene 20灯 Kerosene 20〃 Example 5 Higher ester derivative (E) 40 wt% butyl cellosolve 20〃 Methyl naphthalene 20〃 Kerosene 20〃 Example 6 Heptadecenyl hydroxy hydroxyethyl isidazoline 35 wt% Higher ester derivative (F) 5Ｆ butyl cellosolve 20〃 Methyl naphthalene 20wt Kerosene 20〃 Comparative Example 1 Roto oil 40wt% butyl cellosolve 20〃 methyl naphthalene 20〃 kerosene 20〃 Comparative Example 2 Neugen EA140 40wt% butyl cellosolve 20〃 methyl naphthalene 20〃 kerosene 20〃 Comparative Example 3 Tetronic activator 40wt% butyl cellosolve 20〃 Methylnaphthalene 20〃 Kerosene 20〃 Comparative Example 4 Formalin condensate of polyoxyethylene alkylphenol ether 40wt% butylcellosolve 20wt% Methylnaphthalene 20〃 kerosene 20〃 Comparative Example 5 Dioctyl sulfosulfinate 40wt% butylcellosolve 30〃 Kerosene 30〃 Comparative Example 6 Heptadecenyl hydroxyethyl isidazoline 40 wt% butyl cellosolve 20〃 methylnaphthalene 20〃 kerosene 20〃 (Evaluation method 1) 50% by volume of water was emulsified in heavy oil in the form of an emulsified oil as in Examples 1 and 2 and Comparative Examples 1 and 2. 20 ppm of oil-water separator is added individually, Stir well for 1 minute and then 100ml (almost 50ml of water,
Approximately 50 ml of heavy oil) is collected in a measuring cylinder,
It was left still in a constant temperature water bath.

Table 1 shows the amount of separated water (ml) at the lapse of 10 minutes, 30 minutes, 1, 2, and 4 hours after standing.

(Evaluation Method 2) 90 ml of Minas crude oil was added to 10 ml of water, and the mixture was sufficiently stirred with a homogenizer rotating at 3500 rpm for 1 minute to prepare a large number of crude oil emulsions. Example 3
10 ppm of each of the separation agent mixed liquids of Nos. To 6 was added, and the mixture was stirred for 30 seconds.

Table 2 shows the amount of separated water (ml) after 10 minutes, 30 minutes, 1 hour, and 2 hours after standing.

────────────────────────────────────────────────── (5) References (56) References JP-A-63-278507 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) B01D 17/05

Claims (1)

(57) [Claims] An oil or water containing as a main component a surfactant obtained by addition-polymerizing an alkylene oxide to a carboxyl group of a higher polybasic acid having at least 12 carboxyl groups and having 12 or more carbon atoms in the molecule. Separating agent.