WO1980002432A1

WO1980002432A1 - Process for treating aqueous waste oil

Info

Publication number: WO1980002432A1
Application number: PCT/JP1979/000107
Authority: WO
Inventors: T Yoshimura; M Soeda; H Okazaki; T Yushima
Original assignee: Nippon Steel Chemical Co; T Yoshimura; M Soeda; H Okazaki; T Yushima
Priority date: 1979-05-01
Filing date: 1979-05-01
Publication date: 1980-11-13
Also published as: GB2060597B; GB2060597A; DE2952968A1

Abstract

Process for treating an aqueous waste oil, which comprises adding, to an aqueous waste oil having an aromatic oil content of A defined by the following formula: Aromatic oil content = Weight of aromatic oil component,/Weight of total oil comprising oily component, water and solid component and forming a W/O emulsion, a treating oil having an aromatic oil content of B (provided that B stands outside the range of 0,4(Alpha)B0,6 and 4FA-B4F>0,5) in an amount of not less than 1% by weight based on said aqueous waste oil to thereby separate oil component. This process enables to easily separate an oil component from coal tar or petroleum waste oil.

Description

n

Treatment of water-containing waste oil

Skill field

The present invention relates to a method for treating water-containing waste oil, and in particular, forms a water-in-oil emulsion consisting of oil, moisture and sludge.

Rice field

The present invention relates to a method for treating a water-containing waste oil by adding a specific solvent to the water-containing waste oil.

£ 3 shadow technology

Π — At the ruling mill, distilling of the core oil such as carbohydrate oil, naphthalene oil, cleaning oil, and anthracene oil is carried out. When the oil to be discharged is subjected to treatment such as deoxidation and debasification, etc. f), and used for collecting light oil in coke oven gas, etc. Water-containing waste oil is generated when it comes in contact with water. In addition, water is mixed in the coal tar itself, and waste oil is similarly generated during tank storage and 3-hydroxy distillation. Ο In addition, storage of various oil components 'Waste oil' is also generated when cleaning tanks

3 — Oil derived from rutar has a higher affinity for water than oil derived from petroleum, and easily forms a water-in-oil emulsion ο Water-containing waste oil Although there are slight differences in properties depending on the place where they occur, they usually contain not only oil and water but also sludge, which is solid, and are extremely stable by these three. Emma

ΟΜΡΙ

^ Ii. ^ / Forming a resolution.

If the water-containing waste oil in the tar factory is concentrated ^, the composition of the waste oil is relatively averaged, and the composition is about 10 to 40 weight of oil. The sludge content is 1 to 5% by weight, and the balance is moisture. The sludge includes inorganic substances mainly composed of iron compounds, pitch-like polymers composed of aromatic condensed rings, coke powder, coal powder, etc., and is dry in hydrated waste oil. It swells about 10 times and exists. The oils are mainly benzenes as light components, naphtholines as medium components, and anthracenes as heavy components. It contains cyclic aromatic compounds. The specific gravity of oil is relatively close to that of water, and varies depending on the type of sleeve. However, the specific gravity of oil is lower when the amount of light components is higher and when the temperature is higher.

In addition, rolling process at steelworks, pipe making process, coke oven gas cleaning process using Ishisode-type absorbent oil, rolling waste oil, lubricating waste oil, cleaning waste oil from machinery plants, etc. In the oil refinery and petrochemical plants, the washing process of crude oil tanks and heavy oil tanks, the crude oil waste oil, heavy oil waste oil, tank residue oil, mud oil, etc. A large amount of oil-containing waste oil such as lubricating waste oil, automotive engine oil waste, cutting oil, and anti-mold oil is generated from automobile factories, machinery manufacturing plants, shipyards, etc. These petroleum hydrous waste oils differ slightly in their properties depending on where they are generated, but usually they contain not only pond and water but also solid sludge. It also contains other additives such as emulsifiers. And, they form extremely stable ヱ -marion. For example, a steel mill The waste oil generated from the rolling process, the coke oven gas cleaning process, and the mills is mainly composed of petroleum oils such as rolling oils, lubricating oils, machine oils, and cleaning oils. Water-in-oil type (hereinafter referred to as type 0) consisting of finely divided solids such as mixed oils, water and iron oxides, carbon, etc. O Waste oil, mud oil, etc. generated from the washing process of raw tanks, oil tanks, etc. in stone, oil and refinery plants, or machine manufacturing plants However, the waste oil generated from other places is almost the same as the water-containing waste oil in the form of W0-type emulsion.

The composition of these water-containing waste oils is usually 50% by weight or more of petroleum-based oil, 0.1 to 1.0% by weight of solid content (in terms of dry matter), and the balance being water. Stone oil refers to oil whose main salary is non-aromatic oil. The solid content is prepared by using a metal powder such as an iron powder, an iron compound such as an iron oxide, a power bone, dust or sand. Solid content exists as sludge with oil or water attached o

These tar-based and petroleum-based water-containing waste oils, even if forcibly separated by a centrifugal separator in any case, still have oils and emuls formed at the beginning. The treatment is extremely difficult, since the proportions of ionic, water and solid contents hardly change over time. In addition, since this water-containing waste oil has poor flammability, the erection rate as a fuel is poor, and the sludge also causes a blockage of the chip.

Conventionally, as a method for recovering oil from tar-based hydrous waste oil, a method in which a specific surfactant is added is known.

O PI (Kaisei 51-96, 785). However, this method mainly uses water as an oil component.] Because the main thing is heavy, water separation is good when centrifuged, but slurries are not possible. Separation of ludge from oil is not always good, and satisfactory results have been obtained when one wishes to recover high quality oil or when processing waste oil containing lighter oil than water. Absent.

In addition, as a method of treating an emulsion-type oil-containing waste oil such as the above-described oil-type oil-based waste oil, the waste oil is heated and pressurized, and then cooled. , divided into three layers of oil and water and solids, how to centrifugation layers (JP-B ⁵ 1 - 4 7 7 2 2 No.),豉壊is heated waste oil Interview Ma le di Yo emissions After cooling, the layers are separated (Japanese Patent Publication No. 51-43305). The waste oil is centrifuged under heating to separate oil, water and sludge. A method of further centrifuging the obtained oil and water (Japanese Patent Application Laid-Open No. 51-2123403) has been proposed. However, these methods require a great deal of energy for heating, pressurizing, centrifuging, etc.], but the separation of sludge and oil is not Not enough. Also, after adding a light petroleum fraction to the mud oil and extracting the oil, the resulting deoiled mud oil is heated or treated with a coagulant and centrifuged to separate water and solids. to that method (JP-b-4 7 - 1 ⁵ 0 ² 5 JP), waste oil or the scan rats di in profile pan, to no porcine emissions or profile pan hydrocarbons in diesel fuel until the main . admixing a hydrocarbon solvent shall be the component, how to separate the oil and vinegar rats di minute (U.S. Patent No. 3, 68 ^4, 699 Contact and JP 4 9 -

OMPI

WiPO No. 39601) has been proposed. However, these methods have the disadvantage that the operation is complicated, or that the separation between the sludge and the oil is inadequate. In addition, a method of dispersing the sludge by adding a neutral cholesterol oil in which a small amount of a specific surfactant is dissolved is added to the sludge. (U.S. Pat. Nos. 2,555,5794) has also been proposed, but is not intended for oil / water classification. Therefore, the purpose of the present invention is to provide a novel treatment of waste sleeves containing oil, water and sludge, forming a water-in-oil emulsion. Is to provide the law. Another object of the present invention is to provide a method for recovering oil by treating a water-containing waste oil derived from coal or petroleum-derived waste oil by adding and mixing a specific processing oil with the water-containing waste oil. O The purpose of these disclosures is to provide an oil-water type marion which consists of sleeves, moisture and solids. Amount of aromatic oil represented by the following definition in the method of treating water-containing waste oil: A Aromatic oil weight

Aromatic oil content =

Aromatic oil content B relative to hydrous waste oil having a total oil weight (except for 0.4 ≤ B ≤ 0.6 and IA-BI> 0.5)処理処理処理 1 処理 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 BRIEF DESCRIPTION OF THE FIGURES

Fig. 1 is a graph showing the effect of the amount of kerosene added to the oil content in the coal tar-based water-containing waste oil on the separation index. O This graph shows the effect of adding a solvent and a surfactant to the water content of the coal-tar hydrous waste oil on the difficulty index.o

BEST MODE FOR CARRYING OUT THE INVENTION According to the findings of the present inventors, the ratio of the weight of aromatic oil to the total weight of oil in hydrated waste oil, that is, the aromatic oil content A (hereinafter, hydrated waste oil) The aromatic oil content in the oil is referred to as A.) (However, preferably excluding 0.4 ^ ^ ≤0.6.) The ratio of the weight of the aromatic sleeve to the total weight of the oil, ie, also the aromatic oil content Β (hereinafter, the aromatic oil content in the processing oil is Β). Excluding 0.4 ≤ Β ≤ 0.6 and IA-Β I> 0.5 i), preferably excluding 0.3 but B <0.7 and IA-B |〉 0.7. ), More than 1% by weight, preferably 2 to 100% by weight, and more preferably 5 to 50% by weight, based on the water-containing waste oil. In this way, the highly stable W0 type emulsion described above is broken down and the sedimentation of the sludge is improved, and the separation from water is also improved. Become. This allows the oil to be separated by static separation. Also, centrifugation can quickly remove sludge, and the oil-water mixture after sludge removal can be left still.]

O PI It was found that the surface was clear and the separation of oil and water was good. Here, the aromatic oil is typically derived from aromatic compounds such as benzenes, naphthalenes, biphenyls, and anthracenes. For example, oils with high aromatics content include tar oils, while oils with low aromatic oils have low oil content. is there .

Specific examples of aromatic oils include benzene, trundene, xylene, trimethinolene benzene, tetramethinolebenzen, and ethyne. Rubenzen, styrene, cumene, naphthalene, methylnaphthalene, dimethylnaphthalene, biphenyl, ant Oil is a typical oil such as rasen, phenanthrene, indian, diphenyl methane, dibenzofuran, and fluoren. And then fisted. When the aromatic nucleus is substituted with an alkyl group having a large number of carbon atoms or an alkenyl group, the aromatic nucleus becomes non-aromatic as the properties of the aromatic oil become weaker. If the non-aromatic substituent such as an alkyl group or an alkyl group has 6 or more carbon atoms, the aromatic oil content is calculated. It is hoped that it will be excluded.

In addition, in order to easily calculate the aromatic oil content, it is recommended that the aromatic index obtained by the following calculation be used as a parameter. . In this calculation method,

Description of Bre'nns to f f Chemie 42 378 (1961) ^ Useful.

Aromatic index = Car / C = 1-l ^ X H / C X Hal / H

However, _carc is the source of carbon and total carbon that make up the aromatic nucleus. Child ratio, HZC is hydrogen and the atomic ratio of carbon determined by elemental analysis, H _a l ZH is filed in the atomic ratio of non-aromatic hydrogen and the total hydrogen, Ru thus calculated et al is the following equation.

Hal H = (

1 + 2 XD _ar / Dal (here, D _ar D _a i is, C - a H bond stretching vibration scan Bae click preparative Le absorbance ratio, absorbance Ζ fat aliphatic aromatic coupling (3.3 beta) It is determined by the absorbance of the sexual bond (3.442).)

The aromatic index thus obtained is used as a reference for calculating the aromatic oil content. In particular, when a special oil such as long-chain alkylbenzene or polyalkylbenzene is not contained, the aromatic index is practically calculated as the aromatic oil content. In most cases, the results are correct.

Comparing the various types of processing oils to be added, the aromatic oils were found to be less than the water-containing waste sleeves (Α> 0.5, preferably A> 0.6). The separation effect was unsatisfactory from light oils such as benzene, toluene and xylene to high-boiling oils such as methyl naphthalene oil. However, oil derived from petroleum containing 60% by weight or more, preferably 70% by weight or more of aliphatic hydrocarbons can be converted from light oils such as hexane to C heavy oil. Good separation results up to high boiling oils such as oils. For example, those containing 40% by weight of aromatic hydrocarbons, such as lead-free gasoline, are not suitable, but residual oil obtained by extracting aromatic hydrocarbons from cracked gasoline. Is valid. However, for processing Oil must be liquid at room temperature.

Each of these processing oils to be added exerts a practically sufficient effect, although there is a slight difference depending on the individual in terms of separation effect. In actual use, it is determined by ease of handling, availability, price, etc. From a practical point of view, kerosene, light oil, heavy fuel oil A, etc. are preferred as oil derived from Ishisode. This is extremely advantageous because it can be treated by mixing water-containing waste oils. The amount to be added to the treatment sleeve is selected according to the amount of oil in the hydrated waste oil, the amount of sludge, the treatment conditions, and the treatment equipment. If the difference is 0.0 S or more, the processing oil / water-containing waste oil (weight ratio) is 1% by weight or more, preferably 2 to 100% by weight, and more preferably 5 to 50%. % By weight, but when additives such as specific surfactants are added, generally less is required, and when the difference between A and B is small, generally more must be added . When the specific gravity of the oil component in the water-containing waste oil is higher than that of water, the specific gravity of the oil layer becomes higher than that of water. Therefore, it is necessary to add a low specific gravity solvent for adjustment. The upper limit of the amount added is not restricted in terms of the separation effect, but excessive use is disadvantageous in terms of economy.

On the other hand, a comparison of various processing oils to be added to petroleum-based water-containing waste oils (A <0.5, preferably A <0.4) indicates that aliphatic hydrocarbon-based oils The separation effect was unsatisfactory up to naphtha, kerosene, gas oil and heavy oil.

ΟΛ1ΡΙ However, as a processing oil used in petroleum-based hydrous waste oil, an aromatic oil containing at least 60% by weight, preferably at least 70% by weight of an aromatic hydrocarbon is used. Any one can be used. For example, gas oil obtained by absorbing coke oven gas with absorbent oil, gas oil obtained by fractionating coal tar, or gas oil obtained by fractionating coal tar, for example. Reforming oil obtained by aromatizing petroleum-based naphtha, by these fractionation! ) Obtained crude or refined benzene, tolene, sonorevent naphtha, konoletar; ^ Naphthalene oil, absorbent oil obtained from , Anthracene oil, creosote oil, or a mixture thereof. Among them, aromatic oils mainly containing a fraction having a boiling point of 130 to 2775 C are effective, and in particular, aromatic oils containing 20 to 60% of naphthalene Is valid. Examples of such aromatic oils include residual oils obtained by distilling a fraction from tar kung to xylene.

In addition, as the treatment oil, a coal tar-based water-containing waste oil can also be used. Examples of tar-based hydrous waste oils include, for example, carbohydrate oil, naphthalene oil, washing oil, and enthracene oil at a coal tar plant. There are waste oils obtained by deoxidizing and debasing the oil components distilled out of coal tar by distillation, storage of various oil components, and waste oil from washing tanks.

The amount of these aromatic oils to be added is selected depending on the oil content, sludge amount, treatment conditions, and treatment equipment in the petroleum-based water-containing waste oil. If the difference between A of hydrous waste oil and B of treatment oil is 0.8 or more, treatment oil / hydrous waste oil (weight ratio) is 1

OJV.PI

^W "C % Or more, preferably from 2 to 100% by weight, and more preferably from 5 to 50% by weight. In addition, when an additive such as a specific surfactant is added, the amount can generally be reduced, and when the difference between A and B is small, the amount generally needs to be increased. There is. The upper limit of the amount added is not regulated by the separation effect, but using too much is disadvantageous in terms of economy.

Particularly good results can be obtained by treating the aqueous waste oil with such a treating oil at a pH of 4 to 8, preferably at a pH of 6 to 7.

In addition, quaternary ammonium salt or imidazole derivative is the main component of the coal-tar hydrous waste oil together with the above treated oil. When a cation-based surfactant is used in combination, favorable results can be obtained. Examples of such surfactants include alkyl trimethyl ammonium salt and alkyl hydroxy imide. There are zolin, alkylimidazolin acetate, alkylimidazolin salt and the like. The cation-based surfactant is 100 to 3,000 ppm, preferably 200 to 1,500 ppm, of hydrated waste oil.o

-Also, when a vanionic or nonionic surfactant is used together with the above-mentioned processing oil for petroleum-based water-containing waste oil, the amount of the processing oil added can be reduced. It can be greatly reduced. Examples of the anionic surfactant include a fatty acid base R! CHs COOM (where Ri is an alkyl group having 11 to 17 carbon atoms or an alkylene group).

O PI H WiPo v And M is Na or K. )'S a door re-error data Roh Lumpur § Mi emission scan Le Ho emissions salt or of Na door Li ©-time scan Le Ho emissions醭塩R ₂ S0 ₃ Na (other, R ₂ is 1 carbon atoms An alkyl group of 2 to 18 R ₃

. ), SOaNa (where R ₃ is an alkyl group having 11 to carbon atoms: I 5), SOsNa (where, R ₄

Is an alkyl group having 1 to 4 carbon atoms. ) R ₅ CHCOOH

S0 ₃ Na

(It's another, R ₅ is Ru A Le key Le group der carbon atoms 1 1 to 1 7.) It's R ₆ COOH ₂ S0 ₃ Na (other, R ₆ is 1 1 to carbon atoms

CH ₃

I

It is an alkyl group of 17. ), R ₇ CONHCH ₂ CH ₂ S 0 ₃ Na (where R ₇ is an alkyl group having 11 to 17 carbon atoms.), RsOOCCHSOsNa (however, E ₈ and ₈ total carbon atoms RsOOCCHa

Is an alkyl group of 10 to 20. ), Rig two emission scan Le Ho phosphate salt, higher A Le co Lumpur sulfate We scan. Te Le salts R90S0 ₃ Na (provided that, R ₉ is A Le key Le group having a carbon number of 1 2 to 1 8 ),

, CHSOsNa (where,. And ΙΐΊ are carbon atoms 12

X I 0 "

~: Alkyl group of Γ8. ), Po the Rio key fractionated Chi Le emissions A Le key Rue over Te le sulfate _a (CH ₂ 0) to I _n S0 ₃ Na (other,! Is A Le key Le charcoal atom number of 8 to 1-8 group, n represents Ru integer der of _{1 ~ 2 0), 2 -} . ^ ~ 0 (CH 2 CH 2 0) to I _m S0 ₃ Na (otherwise, ₂ carbon An alkyl group having 8 to 18 atoms, and m is an integer of 1 to 20. And anionic surfactants such as alkyl compounds and citrate esters, poly (oxyethylene) glycol alcohol ethers R is -0 (CH ₂ CH ₂₀ ) _n H (where 3 is an alkyl group having 6 to 30 carbon atoms, and n is an integer of 3 to 120). Poly (oxyethylene) alkyl aryl ether R 1

0 (CH ₂ CH ₂ 0) _n H (where R “is an alkyl group having 6 to 12 carbon atoms, and n is a decimal number of 3 to 120). (O · The fractionated Chi les emission) A Le key Le et scan Te le _{_{R 15 -COO (CH2CH 2 0)}} n H or _{_{R is - COOC CH 2 CH 2}} ) ^^ rjCH 2 CH 2 -COOR 1 5 ( was it, R i ₅ is carbon atom number of ⁶ to ^{2 4} a Le key Le group, n represents Ru Oh ³ to 1 2 0 integer.), Po Li (O key fractionated Chi les emission) a Le Kill Amin R 16-

Z (CH ₂ CH ₂ 0) _n Ii

NH (CH ₂ CH ₂ 0) _n H or R ₁₆ — (However,

R is an alkyl group having 6 to 30 carbon atoms, n and 3

It is an integer of up to 120. ), Po Li (O key fractionated Chi les emission) A le menu CH _₂ CH ₂ 0) _n H § Mi de _{_{R 17 - CONH (CH 2 CH}} 2 0) n H or R _{1 7} - CON:

ヽ (CHsCHzO H

(It's ¾, R ί ₇ is A Le key Le group having a carbon number of ⁶ ~ 3 0, η your good beauty η '3 to:. Oh Ru 1 2 0 integer), Po Li (O key Shea Ethylene-) Sorbitan fatty acid ester _n H

I

0 (CH ₂ CH ₂ 0) _n H

(It's another, Ris is A Le key Le group having a carbon number of ⁶ ~ ² 4, n is Ru integer der of 3 ~ 6 0 o), pull-port double click type Po Li (old key fractionated in Styrene-poly (co-propylene) cocondensate HO (CH ₂ CH20) CH ₃ CHCH ₂₀ ) _b (CH ₂ CH ₂₀ ) (however, a, b fine c with> l (a + b + c ) = 2 0-4 0 0), Te bets port -. Tsu the co-condensation product H (C ₂ H40 clauses _{_{_{type) y (C 3 ¾0) V}}} ( C ₂ H40) y, Η

H (C ₂ H40) y (C ₃ ¾0) _x ,

(C ₂ H4G) y »H

(However, χ ~ χ "'and y ~ y"> l, x + x ^ + x "+ x'" + y + y '+ y' + y ^m

= 20 to 800. ) And other nonionic surfactants. The amount of these surfactants added is usually between 100 and 5,000 pm, preferably between 500 and 2,000 ppm, relative to the hydrous waste oil. The surfactant may be 1 to 10% of a water-soluble aqueous solution, or an oil-soluble surfactant may be a stock solution or a petroleum or coal. It can be added by dissolving it in a tar treatment oil.

^ Need to treat and treat aliphatic or aromatic oils in water waste oil? After adding surfactants, improve contact mixing.

Small ' It is necessary to mix with sufficient agitation to achieve this. Heating is preferred for this mixing. As a mixing method, an appropriate method such as a method of performing circulation by a pump in a tank or a method of using a line mixer may be used. The heating is preferably carried out at a high temperature within a range in which vaporization of the oil and solvent in the waste oil is not a problem, and practically 20 to 90 C, preferably 50 to 70 U. Is good.

After adding and mixing the processing oil for such an aliphatic oil or aromatic oil, the oil is separated when the oil is allowed to stand, or such an aliphatic oil or an aromatic oil is removed. If the sludge is removed by supercentrifugation or the like after adding and mixing the processing oil for the base oil or the aromatic oil, the oil / water separation effect can be further improved. As a method for removing sludge, a centrifugal separation method is preferable. The higher the centrifugal force, the better the separation effect. However, it is usually 800 G or more, and from the economic viewpoint, it is preferably 2,000 to 4,0,0. 0 0 G. When applying this centrifugation, it is preferable to separate the sludge.o

Various types of centrifugation can be used as devices for simultaneously performing sludge separation and oil / water separation.However, a filtration type device is not a surface renewal type. The problem of clogging due to ledges is liable to occur, and it is difficult to completely separate the sludge of the surface renewal type. Therefore, it is preferable to use a centrifugal sedimentation type, and the liquid from which the sludge has been removed by the centrifugal separator is allowed to stand still.

OV.PI Almost no emulsion layer remains at the interface, separated into two layers, an oil layer at the top and a water layer at the bottom, and the oil and water can be easily collected and separated. You. The oil recovered in this way can be used at least as a fuel sleeve, and depending on the source of the waste oil, can be used for more valuable applications. You. On the other hand, water can be purified by activated sludge treatment without special pretreatment because the oil content is only the dissolved amount. Next, the method of the present invention will be described in more detail with reference to examples. The percentages in the following examples are based on weight unless otherwise specified.

Examples 1 to 6 and Comparative Examples 1 to 3-

The aromatic oil (分> 0.9) with a specific gravity and viscosity at 60 C of 1.007 and 2.4 centipoise, respectively, and a Η C ratio (atomic ratio) of 1.015 was 34.7% and a slurry. A water-containing waste oil (a mixture of those generated in a coal tar plant) forming a water-in-oil type emulsion containing 2.3% (dry state) did.

^ 50 m scale made of glass ^ Add 30 ml of the sample and 6 ~ of each processing oil to the centrifugal sedimentation tube, agitate with 6 for 15 minutes, then use the suspended centrifuge And centrifuged at 1,500 G for 15 minutes. When the separated oil layer, aqueous layer and sludge layer in the centrifugal sedimentation tube were measured, the results shown in Table 1 were obtained.

OMPI

,, Purport H

Sukhno ν 7〗 (¾com¾Γ J [¾Α ^ "" 7, i

1 11 Hatsoso 77 Q 1

(CB = 0)

Real 2 n octane 90 82 11 7-8 Al 3 XI {B ο ij o 3 76 10 7.6

4 Light oil C ") 79 88 15 5

5 A heavy oil (〃) 56 85 19 3 6

6 c heavy oil /) 66 82 13 5.9

1 58 86 29 2-5

(B = 1)

2 Methynorenaphthali 19 48 68 0.5

(,,)

An example

3 Gasoline 56 54 19 2.8

(Β 0.5) Note)

Amount of water separated (

Moisture recovery D == X 100

Moisture content in waste oil Separated oil content

Oil recovery (= X 100

Volume m-rn ^ m w Sludge volume o

Sludge layer damage] ^ (z) = X 100

mm (+ m w x + y

Separation index-

2 z The separation effect becomes closer as the water recovery rate and oil recovery rate are closer to 100.

0MPI in. Can be determined to be good. The smaller the sludge layer ratio, the better the sludge is compressed and the easier it is to centrifuge the sludge. When these relationships were unified and arranged in terms of the separation index, the ease of separation matches the actual situation well, and this separation index is large. Good separation inclination

O showing I j

As is clear from Table 1, it can be seen that the processing oil rich in aromatic compounds, in which the difference between A and B is 0.5 or less, has a poor separation effect, especially sludge separation. .

Example 7

In the same manner as in Example 1, kerosene was used as the processing oil, and the relationship between the degree of separation and the amount of kerosene added was determined. .

Figure 1 shows the results.

Example 8

Oil 2S. ^7%, the scan rats di 1 and 2% (dry) water-containing waste oil the balance occurs in Oh Ru data Lumpur factory in moisture (Α> 0 · ⁹⁾ against the 1 0 _W ^S, the kerosene Heat-mixed at 6 for 3 hours in a 2.6 W tank o

'The mixture of this was charged to 0.5 _W ^S Z h centrifugal sedimentation type at a ratio of Γ違心separator (Su - Pa over de Ca te chromatography), ^3, 000 & residence time 1. & ⁴ minutes' treatment Then, it was continuously separated into sludge and liquid. The separated liquid was allowed to stand in a standing tank to separate oil, and oil was recovered from the upper part and water was recovered from the lower part. The resulting vinegar rats di 27.1% moisture, was oil ^{^47.8%.} The recovered oil is 0.3% moisture, sludge

-BU EAU

OP! 1PO 1¾

Minute was 0.06%. The separated water has an oil content of 66 pm, S S

At 20 ppm, it was treated in an activated sludge facility.

Examples 9 to 12

The same sample as in Example 1 in a graduated centrifugal sedimentation tube made of glass

Add 30 m, kerosene 3 ^ and various surfactants 1,000 ppm, stir for 60 C T- 30 minutes, and then use a suspension centrifugal precipitator at 98 G Centrifuged for 5 minutes. Among the surfactants, a water-soluble surfactant was added as a 2% aqueous solution, and an oil-soluble surfactant was added as a 2% kerosene solution. When the separated oil, water and sludge layers in the eccentric sedimentation tube were measured, the results shown in Table 2 were obtained.

—Type of surfactant Water separation Oil separation Sludge

Rate (X) Rate) Rate (Z) index

9 Nono trimethyl 98.0 78.3 11.6 7.6

Salt

10 FANOH hydroxyethylui 97.9 78.3 12.1 7.3

Mida / Lin

11 Danomitimizoline 102.9 76.9 8.7 10.3 Danoremitari ^ 103.2 77.2 8.1 11.1

¹²¹²

Note) Water separation rate D

Moisture separated (£)

X100

»¾f content + field Moisture of S ^ SWf ¹ (experiment with water fiber and L)

Oil separated (m £)

Oil separation rate X .100

M + ocho «amount of settled sludge ^)

Sludge ½ <z> X 100

mm + binding oil, ^

X + Υ

Separation index-

2Ζ

Example 13 'In the same manner as in Example 10, when kerosene, heavy oil and c-heavy oil were used as the solvent, the amount of solvent added and the alkyl hydroxy were used. The relationship between the amount of methyl imidazoline added and the separation index was determined. However, the centrifugal force was 1,250 G. Figure 2 shows the results. Note that each curve represents the next one.

OMPI

1 ^P0 Curve agent Surfactant amount _ (ppm)

A Kerosene 2,000

B Kerosene 1,000

C Kerosene 500

D A 虛 Oil 1,000

E C heavy oil 1,000

Example] 15 and Comparative Examples 4 to 5

4 put that specific gravity ^0.84 2 der and C, elemental analysis C 85.3% s H 13.7% of oil that Yusuke (A tool 0.1) 73%, solids such as moisture 2 6% and iron oxide content (Equivalent to dry state) 1.2% of mixed waste oil mainly composed of petroleum oils such as rolling oil and machine oil and forming W / 0 type emulsion, Predetermined amounts of the processing oil and additives were placed in a 50 CC centrifugal sedimentation tube, and heated for 30 minutes in a 60 C water bath with vigorous stirring. One 1 at stomach suspended centrifuge, 2 ⁵ 0 G 1 5 minute centrifugation min away the performing was o a centrifugal sedimentation tube take out to the oil layer, an intermediate layer of oil layer and an aqueous layer (We Ma Le di ® ), The volume of the water layer and the volume of the sedimentation layer (solids + water) were read. The results obtained by changing the type of additive were as shown in Table 3.

Note 1) Tar-based mixed oil I: Distillation residue of a tar-based light oil with a boiling point of about 140 to 230 C containing xylene, trimethylbenzene, naphthalene, methylnaphthalene, etc. as the main component (B> 0.9). Note 2) Anionic surfactant: di-octyl sulfosuccinate sodium salt. Volume of oil layer after centrifugation x 100

Note 3) Oil separation rate

Amount of processing oil added + oil content in waste oil

Examples 16 to 25 and Comparative Examples 6 to 7

Put that specific gravity 0.835 der to 4 C, elemental analysis C 8 ^{^5. 5%,}

H Lubricant, coke oven gas cleaning oil with 55% oil content 13.2%, water content 44% and carbon-like solids (converted to dry state) 1.5% Is a mixed waste oil whose main component is petroleum-based oil, such as a steel mill waste oil that forms emamulsion (A <

0.2), a centrifugation test similar to that of Examples U to 15 was performed by adding a processing oil and additives. The result is

4 It was as shown in the table.

Four

Note 1) Coal tar oil concealment oil: boiling, ^ J 250 to 300 t: dimethylnaphthalene to near anthracene. Note 2) Anionic surface viability II: sodium salt of octyl sulfosuccinate ester.

Example 26

20% by volume of tar-based mixed oil I in Example 14 and sodium dioctylsulphosuccinate in wastewater of a steel mill having the same composition as in Example 16 The solution to which 2,000 ppm of Pyrium salt was added was heated and mixed at 70 C for 30 minutes. Then, this liquid was subjected to decompression and filtration under the pressure of 250 to 300 cages ZH ^ using a 11G3 glass filter, and it took 150 minutes. Even after the above, ^ ^ was possible, and the liquid volume up to 150 minutes was 73 / ^. The liquid easily separated into oil and water.

Comparative Example 8

When the same method was performed as in Example 26 except that the tar-based mixed oil I was not added, the filter was clogged after about 60 minutes due to clogging of the filter. It became impossible. During this time,

It was 20. ,

Example 27 and Comparative Example 9

Grayed lease-like oil (A <0.1) 88.6% by volume, 7% by volume of your good beauty solids moisture (dry matter basis) Ri ^4.4 Do I vol.%, A specific gravity of about

0.9 Crude data down click scan rats di ² Q m £ of the that data 'was one Le-based oil mixture I or put in Example 1 ⁴ kerosene 2 0 ^ was added and the temperature 8 0 C Except for the fact that after eccentric separation after heating and mixing under the same conditions as in Example 14, the results in Table 5 were obtained.

OMPI Five

In addition, when a similar experiment was performed without using the processing oil, emamulsion was not completely separated.

Example 2 8 to 3 3

Residual oil obtained by distilling a distillate from tar gas oil to xylene from a steel mill waste oil similar to that of Example 14 (B> 0.9) (boiling point: about 140 to 230) Ό) was added to 30% of waste oil and a surfactant, mixed, heated at ⁷⁰ C for 30 minutes, and then centrifuged at 1250 G for 15 minutes. The results are as shown in Table 6.

UREA

OWPI 0 Volume after centrifugation (e.g. amount of addition Oil layer Oil-water middle layer Water layer Sediment

Worried

28 Dodecino w Sensen: ^ 1000 ^pnp 30.0 ^{2-0 6-5} 0.5

Triethanolamine acid

Lamine salt

A

29 Dioctyl: Kono, 1000 29.5 0.5 7.0 2-0

Cuccinate Na salt r

Age

30 Conic acid ester 1000 25.5 5.5 7

31 Dodecino UOfe; Les 1000 23.5 7.0 7-0 1.5

NaHONIC ACID

32 Echile ^ Village Ido 1000 18.0 15.0 4.5 1.5

No

Brohin; de

Age 4

In

33 Sono vt Tanmono Remi 1000 15.0 18.5, 4.0 4.0

Tate Example 3 4 Automobile engine oil's waste oil (composition by centrifugation: oil 91.7 (A <0.1)% by volume, moisture 3.8% by volume, sediment 4.5% by weight) And 0.02 parts of a residual oil obtained by distilling a fraction from tar gas oil to xylene (boiling point: 140 to 230:), dodecinolene benzene 2,000 ppm of acid, sodium hydroxide, and triethanolamine were added, and the mixture was heated and stirred, and then subjected to a centrifugation test o-. As a result, 0.91 part of oil and 0.9% of water 0.04 parts and 0.007 parts of sediment were collected. After addition and mixing, leave it at 80 C for 2 hours.

0MPI

, W1P0 No During the test, a clear oil layer of over 0.7 volume was generated in the upper layer. In addition, after standing at room temperature for 24 hours, the oil layer became more than 0.8 volume.

When only the waste oil was heated and left at 80 C, there was no change even after 2 hours.

Examples 35 to 39 and Comparative Examples 10 to 11

4 Oil with a specific gravity of 0.842 at C and elemental analysis of 85.3% C and 13.7% H (A <0.2) 73% Moisture 26% and solids such as iron oxide (in dry state) ) 1.2% of waste oil and tar that is a mixed waste oil containing petroleum-based oil such as rolling oil and machine oil as a main component and forming wz o-type marjoyon. A predetermined amount of the system-containing aqueous waste oil was charged into a 50 CC centrifugal sedimentation tube, and heated in a 60 C water bath with rapid stirring for 30 minutes. Then, the suspension was centrifuged at 1,2S0G for 15 minutes in a suspended centrifuge. The centrifugal sedimentation tube was removed, and the volumes of the oil layer, the middle layer (emulsion) between the sleeve layer and the water layer, and the water layer and the sedimentation layer (solid content + moisture) were read. The experimental results are as shown in Table 7.

! O.V.PI

, , Is the number of centrifuges; ^ τΚ volume after centrifugation (m Oil separation () or inversion oil reservoir

^ Shear subsidence rate (%)

35 30 tar: 12 24 2 11.5 4.5 90 real 36 30 tar et ^^ Tf ^ ffi 12 24.o 1.0 12.0 4 92

Ayuon surface treatment 37 30 Tarje 12 25 1 12.0 4 94

Nonionic surfactant fj Example 38 12 Tar: C¾ ^ k «30 18 2 17 5 86

39 12 Tar 麵 30 20.5 1 15.5 5 98

10 40 None 1 30 7 2 3 Comparison

Example 11 30 Kerosene 9 1 30 6 2 3 Note 1) Tarue ^ oil: 60g ^ fcg and 1 ~ 007 and 2.4c. Ρ · ¾C ratio (atomic ratio) 1.015 © ½min 34 «%, Duck) contains 2.3% ^« (This is from a coal factory) 9) (Β> 0.8) <Note 2) Anion surfactant (1: Dioctyl sulfosuccinate sodium salt) .

Nonionic surfactant: Propylene Oxide-Propylene Oxide

Surfactant: Alkyl hydroxyshetyl imidazoline o

All have 1,000 ppm excitation. .

Note 3 Volume of oil layer after centrifugation X 100

Oil separation rate (%) =

Additive amount + oil content in waste oil

Example 40

A lubricating oil-based waste oil D (oil (A <0.1) 90.1%, moisture 5.4%, solids 4.5%) mainly composed of petroleum sleeves and a tar mainly composed of aromatic oils Factory water-containing waste oil E (oil (B> 0.8) (produces tar heavy oil with a boiling point of about 20 or more)

8%, water 15%, solid content 3%) to separate oil.

(1) When waste oil D and waste oil E are mixed and released at 7 for 2 hours

Waste oil D Waste oil E Separated oil layer (m)

0 20 0

10 5.5

19 16.5

20

(2) When waste oil D and waste oil E are mixed, centrifuged at 125 G for ¹⁵ minutes, and then centrifuged briefly for oil / water separation.

Waste oil D Waste oil E Surfactant Separated oil layer Emanolescence aqueous layer Sludge (m £) (mi) (ppm) (π &) (mi) (4. (M £)

0 20 Cation 1,000 9-2 9.0 0-0 1.8

10 10 Cation 1,000 17.0 1.6 1.4

20 0 Anion 1,000 14.2 1.0 2.7 2.1

Note 1) Cation: imidazoline-based surfactant.

Note 2) Anion: Alkyl sulfosuccinate sodium salt o Industrial applicability As described above, the method for treating water-containing waste oil according to the present invention is discharged from a coal tar plant or the like. Rolling process and pipe making process at tar-based hydrous waste oil and steel mills, washing process of crude oil tanks and heavy oil tanks at petroleum refineries and petrochemical plants,

Petroleum-based water derived from crude oil, heavy oil, and tank residue

Suitable for use in treating waste oil.

Claims

Scope of Claim 1. A method for treating water-containing waste oils that form water-in-oil emulsions consisting of oil, moisture, and solids. Aromatic oil content A Weight of aromatic oil

Aromatic oil content =

• Total oil weight

A processing oil having an aromatic oil content B (excluding 0.4 ^ B ≤ 0.6 and IA-BI> 0.5) with respect to the water-containing waste oil having A method for treating water-containing waste oil, which involves adding at least 1 weight of the oil to water-containing waste oil and separating the oil.

2. The amount of processing sleeve added to hydrated waste oil is 2 to 100 wt%. The processing method according to claim 1, which is:

3. The treatment method according to claim 2, wherein the amount of the treated oil added to the water-containing waste oil is 5 to 50% by weight.

4. There is a relationship between the aromatic oil content A in the hydrated waste oil and the aromatic oil content B in the treated oil, IA-B |〉 0.7. Claim 1. Processing method.

^{5. The} processing method according to claim 1, wherein after adding the processing oil, the solid content is removed by centrifugation, and then separated into a J3 oil and water by a static separation method. .

^6. The processing method according to claim 5, wherein the heart strength is 800 G or more.

^7. Processing method described in paragraph 1 range of conducted Ru claims at a temperature of the processing oil mixture of addition is 2 0-9.

Ο, 'ΊΡΙ

-A. VV; PO 8. The treatment method according to claim 7, wherein the addition and mixing of the treated oil are performed at a temperature of 50 to 70 ° C.

9. The treatment method according to claim 1, wherein the aromatic oil content of the water-containing waste oil is A <0.4 or A> 0.6.

10. The treatment method according to claim 9, wherein the water-containing waste oil having A> 0.6 is a water-containing waste oil derived from a coal tar.

The processing oil according to claim 10, wherein the processing oil having a ratio of 11B to 0.4 is an aliphatic oil derived from petroleum.

12. The treatment method according to claim 11, wherein the aliphatic oil is selected from the group consisting of kerosene, gas oil, and heavy oil A.

13. A cation-based surfactant mainly composed of a quaternary ammonium salt or imidazole derivative is used together with the treatment sleeve in the water-containing waste oil. The method according to claim 10, wherein 100 to 3,000 ppm is added to the composition.

The treatment method according to claim 9, wherein the water-containing waste oil having a concentration of 14A 0.4 is a water-containing waste oil derived from petroleum.

15. The processing method according to claim 14, wherein the processing oil with B> 0.6 is a aromatic oil derived from coal tar.

(1) The processing method according to the above (15), wherein the aromatic oil is mainly composed of a fraction having a boiling point of from 130 to 275C.

17 ... 'aromatic oil processing methods according to the first ⁶ wherein the claims shall be the Toku徵and this you containing Na full data re down 2 0-6 0% by weight. 18. Aromatic oils range from distillates of coal tar obtained from gas oil collected from the coke oven gas to xylene. 17. The treatment method according to claim ^16, which is a residual oil obtained by distilling a distillate.

19. Claims in which an anionic or nonionic surfactant is added together with the treated oil to the water-containing waste oil at 100 to 5,000 pm. processing method described in the first ⁴ terms.

20. The method according to claim 1, wherein the pH is adjusted to ⁴ to 8 after the addition.

21. The method according to claim 20, wherein the pH is adjusted to 6 to 7 after the addition and mixing.