JPS6333498A - Detergent for sludge - Google Patents

Abstract

(57) [Abstract] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Industrial applications The present invention relates to a cleaning agent for sludge.

Conventional technology and problems Cleaning agents for sludge such as heavy oil and lubricating oil have conventionally been cleaned using oil-soluble solvents, such as petroleum-based solvents such as kerosene and light oil, chlorinated solvents, alcohol-based solvents, glycol-based solvents, etc. Most of them were drugs. Cleaning agents mainly composed of alcohol-based solvents, glycol-based solvents, etc. have poor cleaning properties and are hardly put into practical use except for special uses.

On the other hand, oil-soluble cleaning agents whose main ingredients are petroleum-based solvents or chlorinated solvents elute oil from sludge, remove resinized hydrocarbons, and disperse inorganic components from sludge into the solvent. However, although it is effective in removing oil, it does not necessarily give satisfactory results for sludge with a high solid content because it lacks the ability to disperse solid content. In order to improve this drawback, there is a cleaning agent for slats in which an acid type surfactant is blended into an oil-soluble solvent to improve the dispersibility of inorganic components. Although the cleaning effect of this cleaning agent is superior to those mentioned above, since the solvent used is mainly a chlorinated solvent, there are problems such as skin damage, air pollution, and restrictions on incineration of aging fluids. In addition, when used in combination with acidic surfactants, the corrosiveness becomes significantly high, so it is difficult to use for castings, casings, aluminum, copper, stainless steel, etc.
There are restrictions on the use of tanks or equipment made of iron or other materials.

The above-mentioned problem also occurs in heavy oil tanks, etc., but it becomes a problem particularly when cleaning fixed sludge generated in the rotating body of an oil purifier for removing accumulated sludge of aged lubricating oil and heavy fuel oil.

Oil cleaner sludge is made up of solids that are firmly adhered and deposited inside the rotating body due to the strong centrifugal force caused by the rotation of the rotating body, making it extremely difficult to remove. A combination of a strong chlorinated solvent and an acidic surfactant is used.

As mentioned above, this has problems such as toxicity, skin damage, and corrosion, and there is an urgent need to solve these problems. However, conventionally, the above-mentioned problems have been limited to, for example, the use of corrosion inhibitors and the selection of relatively less toxic chlorinated solvents, and no fundamental solution has been achieved.

In order to solve the above problems, the present inventors first dissolved a chelating agent in water and, if desired, developed a sludge cleaning agent in which a surfactant and a water-soluble solvent were dissolved. No. 60-294595).

Although this cleaning agent shows very good sludge removal effect,
It still takes a considerable amount of time to remove sludge firmly adhered to lubricating oil cleaners, etc., and it is desired to develop a sludge cleaner that can desirably process the sludge in a shorter time.

Means for Solving the Problems The present invention relates to a sludge cleaning agent made by solubilizing or emulsifying the above-mentioned chelating agent and hydrocarbon solubilizer in water, thereby further improving the cleaning effect and reducing the time required for cleaning. can be further shortened.

Examples of the hydrocarbon solvent used in the present invention include petroleum fractions such as kerosene and light oil, paraffins, naphthenic hydrocarbons, and aromatic hydrocarbons such as toluene, xylene, and methylnaphthalene. Preferably, it contains 5 to 95 parts by weight of a fraction having a temperature of 135 to 350°C.

In the present invention, the chelating agent that can be used is not particularly limited, and phosphonic acid-based chelating agents such as ethane-
1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid (also known as 1-hydroxyethylidene-1,1-diphosphonic acid), ethane-hydroxy-1, Acids and their salts such as 1,2-triphosphonic acid, ethane-1゜2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid, aminotri(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid); carboxylic acid; Acid chelating agents, such as dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, speric acid, azelaic acid, and their salts diglycolic acid;
Acids and their salts such as thiodiglycolic acid, oxalacetic acid, oxydisuccinic acid, carboxymethyloxydisuccinic acid, carboxymethyltartronic acid; glycolic acid, malic acid, hydroxypivalic acid, tartaric acid, citric acid, lactic acid, gluconic acid, Acids such as hydroxycarboxylic acids and their salts such as mucic acid and glucuronic acid; itaconic acid, methylsuccinic acid, maleic acid, fumaric acid, glutamic acid, acunitic acid, ethanetetracarboxylic acid, ethylenetetracarboxylic acid, phthalic acid, trimesic acid, hemimelitic acid,
Acids such as pyromellitic acid and benzenehexacarboxylic acid and their salts: sulfoitaconic acid, sulfotricarballylic acid,
Acids such as sulfonated carboxylic acids such as cystic acid and sulfoacetic acid, and their salts; sucrose, lactose, raffinose,
Carboxymethylated niaminopolyacetate-based chelating agents such as pentaerythritol and gluconic acid, such as nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetra,
Acids and their salts such as diethylenetriaminetriacetic acid, glycol ether diaminetetraacetic acid, hydroxyethyliminodiacetic acid, triethylenetetraminehexaacetic acid, etc.: Phosphorus-containing carboxylic acid type chelating agents, such as phosphonobutane-1゜2
-Acids and salts thereof such as dicarboxylic acid, 2-phosphonobutane-2,3゜4-tricarboxylic acid, and phosphonocarboxylic acid; polyphosphates, such as orthophosphate, pyrophosphate, tripolyphosphate, metaphosphate, hexamethalin acid salts, futates, etc.; polymeric carboxylic acid chelating agents such as polyacrylic acid, polyaconitic acid, polyitaconic acid, polycitraconic acid, polyfumaric acid, polymaleic acid, polymethaconic acid, poly-α-hydroxyacrylic acid, Polyvinylphosphonic acid, sulfonated polymaleic acid, maleic anhydride-diisobutylene copolymer, maleic anhydride-styrene copolymer, maleic anhydride-methyl vinyl ether copolymer, maleic anhydride-ethylene copolymer, maleic anhydride -Ethylene crosslinked copolymer, maleic anhydride-vinyl acetate copolymer, maleic anhydride-acrylonitrile copolymer, maleic anhydride-acrylic ester copolymer, maleic anhydride-butadiene copolymer, maleic anhydride- Isobutylene copolymer, itaconic acid-ethylene copolymer, itaconic acid-aconitic acid copolymer, itaconic acid-maleic acid copolymer, itaconic acid-
Acrylic acid copolymer, malonic acid-methylene copolymer, methaconic acid-fumaric acid copolymer, ethylene glycol-
Ethylene terephthalate copolymer, vinylpyrrolidone
Vinyl acetate copolymer, starch succinate, etc.; non-dissociated polymer chelating agent, such as polyethylene glycol,
polyvinyl alcohol, polyvinylpyrrolidone, cold water soluble urethanized vinyl alcohol, etc.; and other chelating agents such as imidosulfates, imidobissulfates,
Examples include diethyldithiocarbamate, ethylxanthate, 1,2-dimercaptopropanol, thiourea, diethyldithiophosphate, ditisone, 8-hydroxyquinoline, and dimethylglyoxime.

Particularly preferred chelating agents are phosphonic acid chelating agents, particularly l-hydroxyethylidene-1,1-diphosphonate, aminotri(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid) and salts thereof, and carboxylic acid chelating agents. chelating agents, especially hydroxycarboxylic acids, such as citric acid, glycolic acid, tartaric acid, dicarboxylic acids, oxalic acid, succinic acid, and salts thereof. Furthermore, each acid, salt, etc. may be blended.

The chelating agent may be used in the free acid form, but may also contain alkali metals such as sodium, potassium, etc., alkanolamines such as monoethanolamine, jetanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, etc. Amines, triisopropanolamine, methylethanolamine, ethylisopropanazine, etc., primary, secondary or tertiary amines and unneutralized products of their ethylene oxide or propylene oxide adducts or quaternary amines, ammonia It may be neutralized by Neutralization of the chelating agent not only maintains or improves cleaning performance, but also improves anticorrosion properties, making it possible to use it for tanks and equipment made of various materials.

The blending amount of the chelating agent and hydrocarbon solvent is 1 to 40 for the former.
% by weight, preferably 2-30% by weight, the latter 1-50% by weight
%, preferably 2 to 20% by weight.

A suitable surfactant is blended to solubilize or emulsify the chelating agent and the hydrocarbon solvent.

Nonionic surfactants, anionic surfactants, amphoteric surfactants, etc. can be used as surfactants. Depending on the type of chelating agent, cationic surfactants may be used, but nonionic surfactants and anionic surfactants can be used. Surfactants are particularly preferred. A combination of multiple types of surfactants may be used.

Specific surfactants that can be used in the present invention.

Examples include alkylene oxide adducts of nonylphenol, alkylene oxide adducts of higher alcohols, alkylene dalicol esters of higher fatty acids, alkylene oxide adducts of sorbitan fatty acid esters, alkylene oxide adducts of polyglycerides, and alkylene oxide adducts of styrenated phenols. alkylene oxide adducts (especially Ethylene oxide adducts are preferred, to which propylene oxide may be added to suppress foaming, or phenol-type products may be formalin condensed), higher fatty acids and polyalkylene glycols (e.g. polyethylene glycol ( PEG200-6000, etc.), polyethylene glycol/polypropylene glycol copolymer, etc.)
, esters with polyhydric alcohols such as pentaerythritol, sorbitan, and glycerin, alkanolamide condensates of higher fatty acids and jetanolamine, block or random copolymer rings of ethylene oxide and propylene oxide; dialkyl as anionic surfactants. Sulfosuccinate, alkylbenzene sulfonic acid (salt), sulfuric ester salt of alkylphenol oxide alkylene oxide adduct, sulfuric ester salt of styrenated phenol or its alkylene oxide adduct, sulfuric ester salt of higher alcohol, sulfuric acid ester salt of higher alcohol oxidized alkylene adduct ester salt,
Examples include petroleum sulfonic acid, lignin sulfonic acid (salt), naphthalene sulfonic acid (salt), sulfonic acid (salt) of a formalin condensate of naphthalene, and funnel oil.

Examples of the alkali used in the salt include alkali metals, ammonia, and alkanolamines.

Ethylene oxide is particularly preferred as the alkylene oxide, but propylene oxide or an ethylene oxide/propylene oxide copolymer may also be used.

Surfactants generally have an HLB of about 4-30, and excellent solubilization or emulsification is often achieved by blending a surfactant with a low HLB and a surfactant with a high HLB.

The amount of the surfactant to be blended is not limited, but it is used in an amount equal to or more than the amount of the hydrocarbon solvent to be solubilized or emulsified. Of course, if it can be solubilized or emulsified at a lower amount, it may be used at a lower amount.

Suitable solvents, particularly water-soluble solvents, may be added to the sludge cleaning agent of the present invention in order to improve cleaning properties.

The water-soluble solvent increases the solubility of the chelating agent, suppresses the foaming property of the cleaning agent, and further improves the cleaning effect. These water-soluble solvents include lower alcohols such as methanol, ethanol, isopropanol, alkylene glycols such as ethylene glycol, propylene glycol, diethylene glycol and their ethers and esters such as ethyl cellosolve, butyl cellosolve, ethyl carpitol, Examples include butyl carpitol, ethyl cellosolve acetate, ethyl carpitol acetate, and the like.

Alcohols with low solubility in water, such as butanol, amyl alcohol, hexyl alcohol, cyclohexal, and methyl ethyl ketone, are useful as solubilization aids, and these may be added to improve the stability of solubilization. . Furthermore, lower fatty acids to higher fatty acids may also act as solubilization stabilizers.

The above-mentioned components may be sold mixed with water, or may be added to water at the time of use. As mentioned above, the suitable concentrations are approximately 2 to 20% by weight of the hydrocarbon solvent and 2 to 30% by weight of the chelating agent.

A particularly preferred sludge cleaning agent in the present invention is a solubilized type. A solubilized type has better cleaning properties than an emulsified type, and can be used while operating an oil purifier. When the emulsified type is used while an oil purifier is running, it separates into an oil phase and an aqueous phase due to centrifugal force. Therefore, in order to expect sufficient cleanliness, the disc must be removed from the oil purifier before use.

The sludge cleaning agent of the present invention is particularly useful for removing oily sludge from heavy oil tanks, crude oil tanks, oil purifiers, and the like.

Examples will be described below.

In addition, in the Examples and Comparative Examples, contaminated disks were extracted from two types of oil purifiers and four oil purifiers that were actually operated to clean two types of lubricating oil and two types of fuel oil, respectively, and they were cleaned to the same extent. A dirty disc was selected and used for the evaluation test.

Remove the disks from two types of oil washer machines, Gravitrol type (1) and Selfzetter type (It), which are used to clean the four types of oil shown in Table 1. Select oil cleansing f again! I set it on the plane. The cleaning solution was circulated while operating the oil cleaner, and after a certain period of time, the disc was taken out again and the dirt on the disc was visually observed. The temperature of the cleaning solution at the start of the test was 50°C.

The formulation of the cleaning solution is as follows.

Formulation I Heavy part Nitrilotriacetic acid disodium salt 2.5 Methylnaphthalene 2.5 Dodecylbenzenesulfonic acid tri-5 Ethanolamine salt Funnel oil amine neutralization 5 Water
85 prescription
■ Part by weight ammonium citrate
2.5 Dodecylbenzenesulfonic acid triIO ethanolamine salt methylnaphthalene 25 water
85 Prescription ■ Part by weight Citric acid triethanolamine salt 5 Kerosene
5 Dodecylbenzenesulfonic acid tri
10 Ethanolamine salt butyl cellosolve 5 Diethylene glycol monoethyl 5 Ether water 7
゜Prescription ■ Parts by weight Nitrilotriacetic acid disodium salt 2.5 Methylnaphthalene 25 Dodecylbenzenesulfonic acid tri 10 Ethanolamine salt Polyoxyethylene nonylphenyl 5 Ether (
PI3) Diethylene glycol monoethyl 5 ether water 75
Prescription ■ Parts by weight Ethylenediaminetetraacetate 52 Sodium salt methylnaphthalene 5 Sodium dodecylbenzenesulfonate 10 Butyl cellosolve
6 water
74 Prescription ■
Part by weight Nitrilotriacetic acid disodium salt
5 Methylnaphthalene 5 Dodecylbenzenesulfonic acid tri-10 Ethanolamine salt butyl cellosolve 5 Diethylene glycol monoethyl 5 Ether water 70
Prescription ■ Heavy potassium tartrate 5-methylnaphthalene
5 Dodecylbenzenesulfonic acid tri 10 Ethanolamine salt butyl cellosolve 5 Diethylene glycol monoethyl 8 Ether water 6
7 Prescription ■ Heavy bottle part Hydroxyedylidene-1,1-5 Soditylnaphthalene diphosphonate 5 Dodecylbenzenesulfonic acid tri! 0 Ethanolamine salt butyl cellosolve 5 Diethylene glycol monoethyl 5 Ether water 7
゜Formulation IX Parts by weight Ammonium aminotrimethylenephosphonate 5 Methylnaphthalene 5 Dodecylbenzenesulfonic acid trilO ethanolamine salt Butyl cellosolve 5 Diethylene glycol monoethyl 5 Ether water 70
All of the above formulations showed solubilization (including the semi-solubilized state).

The cleaning effect is shown in Table 1.

The cleaning effect was evaluated in the same manner as in the examples using a sludge cleaning agent containing no hydrocarbon solvent with the following formulation.

Sodium diphosphonate Sodium dodecylbenzenesulfonate 5 water
85 prescription
B Part by weight Ethylenediaminetetraacetate 52 Sodium ethylcarpitol IO Sodium dodecylbenzenesulfonate 5 Water
80 Prescription C Part by weight Methylnaphthalene 85 Dodecylbenzenesulfonic acid tri5 Ethanolamine salt Polyoxyethylene nonylphenyl 10 Ether
EO7*' Formulation D Parts by weight Ethylenediaminetetraacetate 52 Sodium dodecylbenzenesulfonic acid tri-IO ethanolamine salt Butyl cellosolve 5 Diethylene glycol monoethyl 5 Ether water 75
Prescription E Xylene 100 Prescription F Kerosene 100 *' EO7 means 7 moles of added ethylene oxide.

Evaluation criteria Metal surface appearance 50% or less × 〃 50-90% △ 〃 90-95% O〃 95
~ or more ◎ Table 1 Effects of the Invention When the sludge cleaning agent of the present invention is used, it has an excellent ability to disperse the solid content of sludge and has excellent sludge disintegration ability, compared to the case where a conventional petroleum solvent is used alone. Also, since it is solubilized or emulsified in water, the risk of ignition is extremely low.

Furthermore, it contains a chelating agent and a surfactant, etc.
The present inventors filed an application earlier (Japanese Patent Application No. 1983-294595)
The cleaning effect is even better than that of the previous invention.

Claims (1)

[Claims] 1. A sludge cleaning agent made by solubilizing or emulsifying a chelating agent and a hydrocarbon solvent. 2. The hydrocarbon solvent has a temperature of 135 to 350°C.
The sludge cleaning agent according to item 1, containing 95% by weight. 3. The sludge cleaning agent according to item 1, wherein the chelating agent is a phosphonic acid-based chelating agent. 4. The sludge cleaning agent according to item 1, wherein the chelating agent is a carboxylic acid chelating agent. 5. The sludge cleaning agent according to item 1, wherein the chelating agent contains a phosphonic acid chelating agent and a carboxylic acid chelating agent. 6. The sludge cleaning agent according to item 1, which contains a chelating agent in an amount of 2 to 30% by weight of the total cleaning agent. 7. The sludge cleaning agent according to item 1, which contains 2 to 20% by weight of a hydrocarbon solvent.