HUT75012A - Process for investigation on the spot acid content of hydrocarbon-derivatives - Google Patents

Abstract

In the process according to the invention, a given volume of test tube containing a specified amount of alkaline alkali material, preferably alkali metal hydroxides, alcoholates, phenolates, carboxylates or organic bases, or salts thereof with organic acids, and one or more acid-base indicators in an organic solvent mixture comprising the oil to be tested is miscible, the amount of oil allowed by the volume of the test tube is added. In the oily phase, the presence or change of the indicator color indicates that there is less or more oil in the oil than the equivalent of the alkaline material measured for the given volume of oil. In the case of dark oils where the color change or persistence is not evident, water is added after the reaction, the test tube is shaken and the color is examined after the aqueous phase is separated. With an appropriately chosen two-stroke indicator or a mixture of indicators, it can be determined that the aggressive acid content or only the carboxylic acid content exceeds the permitted limit.

Description

Procedure for the on - site verification of the acidity of hydrocarbon derivatives

László Kótai Chemical Engineer, Aszaló, 3841, Honvéd u. 9th

The inventor is the same as the applicant.

The present invention relates to a process for the preparation of hydrocarbon derivatives, such as lubricants, propellants and lubricants. for quick and easy on-the-spot testing of aggressive and total acidity of hydrocarbon mixtures used for other purposes.

It is a known fact that lubricants subjected to various stresses, e.g. increases the carboxylic acid content in motor oils through oxidation processes during use. It is also known that the purification and desulphurisation of hydrocarbon derivatives and / or sulfur derivatives. acid resins or sulfuric acid from the sulfuric acid used in the process during illegal fuel oil treatments; residual sulfuric acid may contaminate the product.

In view of the above, it is important to check the acid content of the fuel to be purchased quickly before purchase. quick routine inspection of lubricants in use.

The present invention is based on the discovery that by treating a given amount of hydrocarbon derivatives with a known amount of an alkaline solution in a suitable solvent comprising a properly selected indicator or mixture of indicators, the acid or mixture at changes, allowing the detection of exceeding the acid limits.

In the process of the present invention, it is not the absolute value of the acid content that is examined, but the maintenance of the acid content within a certain limit or exceeding that limit. In addition, the alkaline substance and / or By selecting an indicator or a mixture of indicators, it is possible to set an arbitrary acid content limit, preferably within the limits of current valid standards.

In the process of the present invention, a known volume of a test tube is placed in a solution of a known amount of a basic alkali hydroxide, organic nitrogen base or alkaline reacting salts (e.g., alkali metal alcoholates, carboxylates) in a suitable solvent and a suitably selected indicator or indicator mixture. The amount of alkaline substance is selected so that its equivalence is within the limits of the acid content allowed by the standards for the amount of oil that can be filled into the test tube. In the choice of solvent - which is aromatic and non-aromatic (up to _C10 ) - branched and open-chain hydrocarbons, chlorinated hydrocarbons, alcohols, water and the like. polar organic solvents such as acetonitrile, dioxane, tetrahydrofuran, dimethylformamide, dimethylsulfoxide, and the like. mixture, we take into account that oil

depending on its quality, whether we want to investigate a mixed or a separate phase system. The indicator or indicator. The indicator mixture is selected according to the pH equivalent of the particular acidic substance to be tested in the particular solvent mixture. As an indicator, acid-base indicators and the like. mixtures of these are used.

US 3,653,838 and EP 170,466 operate on a principle similar to that of the present invention for the determination of the base content (excess alkali in acidification of acids with alkaline agents). The closest solution to the present invention is disclosed in U.S. Patent No. 3,811,837. , which tests the acidity of motor oils using two test solutions, one of which is a measuring solution containing an alkali hydroxide alcohol (ethyl, methyl or isopropyl alcohol) and the other is an indicator solution containing benzene or toluene in addition to the above alcohols. contains an indicator of phenol red, phenolphthalein, cresol red, bromothymol blue, congo red, chlorophenol red or orange I.

The indicator solution is poured into a known amount of alkaline solution and a known amount of oil is added to the resulting mixture which is shaken and the indicator solution is shaken.

- which forms a separate phase from the oil - a change in color indicates whether the acid content of the oil tested is greater than the equivalent of alkaline.

The disadvantages of this procedure are:

- uses two instead of one test solution;

- with the use of an indicator - since it indicates the color signal in a separate phase - it is not possible to simultaneously measure the acid components of different nature simultaneously, such as of carboxylic acids and. sulphonic acids, due to the different distribution of these acids, between the oily and the measuring phase;

The advantage of the process of the present invention over the above-mentioned process is that a single test solution is used which is suitable for the appropriate oil type or oil. provides the information you want to measure with a single quick measurement using appropriate indicators for the parameter (s) you want to measure.

C -

- by selecting the solvent, it is possible to examine the color of the oil-miscible phase, not the separated phase, i.e. to examine the total mass of the initially light (yellow) oil, thereby better detecting the color change and eliminating the partition error.

- In the case of dark oils, a small amount of water is added to the color after the test reaction to evaluate the color - however, a significant difference from the above procedure is that the reaction between the oil and the reagent takes place in one phase and indicator form - the alkaline or acidic form - is extracted only into the oil-separated phase.

Without limiting the scope of the protection, the composition of a test solution for testing a sample of diesel oil is described:

Example 1

Gas oils can contain both naturally occurring naphthenic acids and sulfonic acids left over from sulfuric acid treatment, so that an indicator mixture is suitable for measuring strong and weak acids and, given the light color of the gas oils, it is advisable to choose a solvent mixture homogeneous with gas oil.

A 3: 1 mixture of ethanol-benzene is used as solvent for the above purposes;

Potassium hydroxide, which reacts with both sulfonic and naphthenic acids, was used as the alkaline agent;

The indicator used was a 1: 1 mixture of methyl red and indigo carmine (0.1 g for 100 ml standard solution), which gives the following color gradient:

Methyl red (MV): acidic color: red, alkaline color: yellow: pH equivalent: 4.4 Indigo armin (IK): acidic color: blue, alkaline color: colorless, pH equivalent: 11.6

The following color gradients are observed for the 1: 1 mixture:

1., The total acidity is below the acid equivalent of KOH;

MV yellow

IK is colorless

The resulting color is yellow, ie the original color of the test solution is retained and the acid content of the sample is below the limit corresponding to the KOH equivalent for a given volume of oil.

2., Aggressive acid content exceeding the permitted acid content limit;

MV red

IK blue

Resulting color: purple (in this case the oil is clearly bad)

3., Aggressive acid content is not present, but naphthenic acid content is above limit.

MV: Yellow

ICs resulting color: green

Evaluation:

Case 1 is clearly an oil suitable for the test

Case 2 was a bad oil for the test

Case 3 is a non-standard oil but has no aggressive acid content.

Example 2

In addition to naphthenic acids, the following test may be carried out to determine the limit of aggressive acidity for light oils:

The composition of Example 1 is used in all except that the carboxylic acid salt, preferably sodium dichloroacetate, is used as the alkaline agent. During this test, sodium dichloroacetate reacts only with aggressive acids, not with carboxylic acids, and has a pH equivalent (hydrolytic) above the breakpoint of the indicator, thus only measuring aggressive acids.

This indicates the appearance of blue in the indicator composition of Example 1. If the blue color does not appear, the aggressive acid content is below the limit tested.

Example 3

For dark lubricating oils, the procedure was as in Example 1, but after the test, 1-2 ml of water was added to the test tube, shaken, and after separation the color of the lower phase was examined.

- h -

Example 4

In each case, we used the same procedure as in Example 1, using thymol blue as an indicator, which would double as a function of acid content:

1-3. case as in Example 1:

Case 1: Blue

Case 2: red (the magenta)

Case 3: yellow

Example 5 We used the same procedure as in Example 1, using malachite green as an indicator:

Case 1: colorless

Case 2: yellow

Case 3: green

Note that when using this indicator, the change from colorless to blue indicates the presence of acids, but the amount is below the legal limit. This indicator is also suitable for demonstrating the presence of acid when a basic substance is not used in the test tube, but the solution of the indicator is treated with an alcoholic solution until it becomes colorless.

ó.Példa

All were prepared as in Example 1, but alizarin (1,2-dioxyananthraquinone) was used as an indicator.

case: purple

Case 2: yellow

Case 3: Violet

The following are indicators that can be prepared either alone (to determine the content of a component, e.g. with equivalent conversion range (solvent dependent):

Name of indicator pH range acidic basic Picric acid 2,4,6-trinitrophenol 0.0 to 1.3 colorless yellow methyl Green 0.1 to 2.3 yellow teal

hexa and pentamethyl monoethyl p-rosaniline

Mauvein 0.1 to 2.9 yellow violet N-p-Aminophenylamino tolyl-dimetilfenazin sulfate methyl Violet 0.15 to 3.2 yellow violet tetra- and pntamethyl-p-rosanyl chloride safranin 0.3-1.0 blue red diamino-N-fenildimetil fenazinklorid gentian violet 0.4 to 2.7 yellow violet crystal violet 0.8-2.6 green blue hexamethyl-p-rozanilin chloride Metanilsárga 1.2-2.3 red yellow 4'-anilinazobenzol-m- sulfonic acid, Victor yellow, tropeoilin G m Krczolbíbor 1.2-2.8 red yellow m krezolszulfoftalein thymol blue 1.2-2.8 red yellow Pentametoxivörös 1.2-3.2 violet colorless 2,4,2 ', 4', 2 "-pentametoxi-triphenylcarbinol Tropeolin OO 1.3-3.2 red yellow

4-Phenylaminobenzene-4-sulfonic acid, diphenylamine orange, orange G, orange N, orange IV, aniline yellow, acid yellow O.

β-dinitrophenol 2,6-dinitrophenol 1.7 to 4.4 colorless yellow Benzilnarancs 1.9-3.3 red yellow

4'-Benzylaminobenzenesulfonic acid K salt, benzyl orange

a-dinitrophenol 2,4-dinitrophenol 2.0-4.7 colorless yellow Bcnzopurpurin 4B 2.3 to 4.4 violet red Dimethyl yellow 2.9-4.0 dimethylaminoazobenzene, methyl yellow, butter yellow red yellow bromphenol 3.0 to 4.6 yellow blue

3,3 ', 5,5'-tetrabrómfenolszulfoftalein

Bromochlorophenol blue 3.0-4.6 3,3'-dibromo, 5,5 diklórfenolszulfoftalein yellow magenta Congo red 3.0-5.0 blue red diphenyl-4,4'-bis (azo-2-naphthylamine-4-sulfonic acid l) Methyl orange 3.1-4.4 red yellow α-naphthyl red 3.5-5.7 red yellow

α-naphthylaminoazobenzene p-ethoxyquizoidoid 3.5-5.5

4-ethoxy-2, ', 4'-diaminoazobenzene onion red lemon yellow

Aliza is red 3.7-4.2 yellow red bromocresol green 3.8 to 5.4 yellow blue 3,3'-5,5'-tetrabromo- m-cresolsulfophthalene, bromocresol blue ε-dinitrophenol 2,3-dinitrophenol 3.9 to 5.9 colorless yellow γ-dinitrophenol 2,5-dinitrophenol 4.0 to 5.8 colorless yellow δ-dinitrophenol 3,4-dinitrophenol 4.3 to 6.3 colorless yellow methyl red 4.4 to 6.2 red yellow

4'-dimetilaminoazobenzol-2-carboxylic acid

Ethyl red 4.4-6.2 4'-dietilaminoazobenzol-2-carboxylic acid red yellow carminic 4.8 to 6.2 yellow violet Chlorophenol red 4.8-6.4 3,3'-dichloro-phenolsulfophthalene yellow red p-nitrophenol 5.0-7.0 colorless yellow Azolitmin (litmus) 5.0-8.0 red blue Brómfenolvörös 5.2 to 6.8 yellow red

3,3'-diklórfenolszulfoftalein

bromocresolpurple 5.2 to 6.8 yellow purple 5,5'-dibromo-o-krezolszulfoftalein p-nitrophenol 5.6 to 7.6 colorless yellow bromothymol 6.0 to 7.6 yellow blue 3,3'-dibromo-thymol sulfophthalenes Brómxilenolkék 6.0 to 7.6 yellow blue Nitrazinsárga 6.0-7.0 yellow blue-violet Brazil (Blue tree extract) 6.0-8.0 colorless pink phenol red Phenolsulfophthalates 6.4 to 8.2 yellow red Rozolsav 6.8-8.0 yellow red p-kinonmono (bis-4 · phenylmethyl-oxy) (dioxifukszin) Neutral 6.8-8.0 red yellow 3-Amino-6-dimethylamino-2-metilfenazinklorid m-nitrophenol 6.8-8.6 colorless yellow

hematoxylin 7.0 to 11.0 yellow violet a-naftolftalein 7.3 to 8.7 colorless orange Curcuma 7.4-8.6 yellow brown brilliant Yellow 7.4-8.6 yellow brownish red Tropeolin OOO 7.4 to 8.9 yellowish green pink

α-naphthoazobenzene-p-sulfonic acid, α-naphthol orange, orange I

Naphthol blue a-naphthol sulfophthalene 7.5-9.0 yellow blue Ethyl bis (2,4-dinitrophenyl) acetate 7.5 to 9.1 colorless blue Xilenolkék p-xilenolszulfoftalein 8.0 to 9.6 yellow blue Indofenoi 8.1 red blue o-Cresolphthalein di-o-Cresolphthalides 8.2 to 9.8 colorless red-violet phenolphtalein di-p-dioxidifenilftalid 8.2 to 10.0 colorless purple o'-naphthol-benzidine 8.9 to 11.0 colorless glaucous thymolphthalein 9.3 to 10.5 colorless blue Blue water 9.4 to 14.0 blue (red) colorless a-naphtholbenzein 9.8 to 11.6 yellow green Alizarin Yellow GG 10.0 to 12.1 light yellow buff

4'-Nitro-4-oxyazobenzene-3-carboxylic acid, salicyl yellow, methachrome yellow

Alizarin Yellow R 10.0-12.1 Light yellow to brownish red

4'-Nitro-4-oxiazobenzene-3-carboxylic acid, alizarin yellow G

• ·

Nile Blue A

10.2-13.0 blue violet red β-naphthol violet

10.6-12.0 orange violets

Nitramin 10.8-13.0

2,4,6-Trinitrophenylmethylnitramine is a colorless brown

Azole violet 11.0-13.0 o-p-dihydroxyazo-p-nitrobenzene yellow violet

Tropeolin O 11.1 - 12.7 yellow violet

2 ', 4'-dioxiazobenzene-4-sulfonic acid, tropeoline R, chrysoidin, resor zinc yellow, yellow T, golden yellow

Indigo carmine 11.6-14.0 Indigo-5,5'-disulfonic acid blue colorless s-Trinitrobenzoic acid 12.0-13.4 colorless orange

Two-stroke indicators:

m Krczolbíbor (M krezolszulfoftalein) 1.2-2.8 7.4 to 9.0 1 red yellow yellow crimson thymol blue 1.2-2.8 red yellow timolszulfoftalein 8.0 to 9.6 yellow blue cresol 0.2 to 1.8 red yellow (P-krezolszulfoftalein) 7.2-8.8 yellow purple Olympic green 0.0-2.0 yellow green 11.5 to 14.0 blue colorless

(Tetramethyl-di-p-diamino-fukszinklorid

Alice Rin 5.5-6.8 yellow violet 10.1 to 12.1 violet purple

1,2-dioxiantrakinon

Claims (4)

Claims 1. A method for the rapid determination of the aggressive and total acidity of hydrocarbon derivatives, wherein a known amount of alkaline material and a suitably selected indicator are added to a test tube to perform the assay, and a suitably selected solvent is added to the mixture to which the volume of the test tube is added. the oil to be examined, seal the test tube, shake the mixture, and change the color of the indicator in the oily phase. determine the relative amount of acid in the test oil. 2. A process according to claim 1, wherein the test tube is used as an alkaline material for the clear and rapid reaction of the acids to be measured with hydrocarbons, preferably alkali or alkaline earth metal hydroxides, or hydrolysis (solvolization) materials with alkaline reaction. oxides, carbonates, carboxylic acid salts, alcoholates or phenolates, organic nitrogen bases or salts of nitrogen bases with organic acids.) 3. A method according to claim 1, characterized in that organic materials, preferably acid-base indicators, which change their color (or lose it) in the presence of acids or bases, alone or in the form of mixtures thereof, are used as indicators. Process according to claim 1, characterized in that the following substances are used as solvents, either alone or in the form of mixtures with each other: aromatic hydrocarbons, preferably toluene, benzene, or xylenes ^C 1 ^-C 10 polyhydric alcohols, preferably methanol, ethanol, isopropanol, glycol or glycerol Open and branched non-aromatic hydrocarbons up to 10 carbon atoms Chlorinated organic solvents, dichloromethane, chloroform, CCl ₄ , trichlorethylene, 1,2-dichloroethane, chlorobenzene Polar aprotic organic solvents, dioxane, tetrahydrofuran, acetonitrile, nitromethane, nitrobenzene, dimethylformamide and dimethylsulfoxide 4. A method according to claim 1, wherein the dark hydrocarbon derivatives, wherein the color change of the indicator in the oily phase, or the reflux of the hydrocarbon derivative is reduced. trace, can be traced in the test tube after performing the test reaction in small amounts, preferably 5-6% (about 0.5 ml of water or other polar solvent is added to a 10 ml test tube, and after separation of the phases the light (non-oily) phase color.